Strategic Management for Smirnoff Assignment Example | Topics and Well Written Essays - 4000 words

Strategic Management for Smirnoff - Assignment Example Smirnoff is a brand of Vodka used in UK and is own and operated by British Company Diageo however, it has its roots in Moscow Russia. Smirnoff is now distributed in well over 130 countries with a network which is expanding and catering to the needs of different customers all over the world. Being an alcoholic drink, the overall external environment for this brand is relatively challenging considering the fact that many countries have banner alcoholic drinking. Issues like the underage selling, drunk driving and other strategic issues are considered as of significant importance. This is because these issues can actually affect the overall demand of the product. This report will look into the target market, value given by the company to its target market, a closer analysis of the internal as well as external environment including analysis of the industry as well as competition. This report will also look into the SWOT analysis of the firm to unearth strategic issues faced by the firm a nd what strategic options could be exercised to correct the situation. Company Background Smirnoff is a brand name managed by a British Company with the name of Diageo. It is however, important to note that Smirnoff as a brand has its historical roots in Russia when during 19th Century, Smirnoff as a vodka brand was started by Pytor Aresenievich Smrinoff. (Diageo Inc) Over the period of time, brand gained recognition and is now considered as the leading vodka brand in the world. What is also important to understand that Smirnoff was the only vodka available outside the communist countries after the Second World War? This therefore has given an edge to the brand to dominate the European and North American market and become the leading selling brand in the world. The company owning and operating this brand is also selling other brands which are also maintained as the strategic brands. These strategic brands therefore serve as the primary source of growth for the firm across all the ma rkets it operates. Some of the leading brands of Diageo include Johnnie Walker, Crown Royal, J&B etc. Smirnoff is also one of the strategic brands for the firm generating the required growth for the firm in the Spirit market.1 It is important to note that Smirnoff exists as a separate strategic business unit for the firm and it is sold through different channels. Delivery of the product through online market of the firm is also one of the ways firm manages sales for this brand. Target Market of the Company Diageo is considered as the premium drink company offering high worth brands to the individuals all over the world. As such the geographical distribution of the company’s target market is across the whole world with concentration in the European and North American market. It is critical to note that the drink market continuously evolve due to the market innovation and changing preferences of the customers. (ASIMOV, 2005). Though Diageo is a well diversified company with man y brands serving different niches in the drink market, however, Smirnoff caters to a different niche of the market. Though Vodka is famous for its uniqueness as a drink however, firm has been able to introduce new flavored drinks in order to cater to the needs of varying degree. The essential market for the drink comprises of those individual customers looking for ready to drink market with variety offered according to the Season of the year. This is because of

Why was Intel initially successful in DRAMs Assignment

Why was Intel initially successful in DRAMs - Assignment Example Dennard claims he went home and formulated the basic idea for DRAM within a few hours, as Mary Bellis explains, â€Å"Dennard and his team were working on early field-effect transistors and integrated circuits, and his attention to memory chips came from seeing another team's research with thin-film magnetic memory. Dennard claims he went home and within a few hours had gotten the basic ideas for the creation of DRAM.† Within two years after its release, Intel would become a world leader in DRAM technologies. Intel created the Memory Systems Operation to assemble the DRAM chips to standards required for sale to OEM’s (Original Equipment Manufacturers), who then put the chips into more sophisticated machines. This operation allowed Intel to distribute their technologies to a wider area. This strategy, in conjunction with offering replacement parts for mainframe computer memories, allowed them to gain more control over the market. Over ninety percent of Intel’s rev enue was brought in by their DRAM, which was the world’s largest selling semi-conductor. Always being the first into new markets, Intel used that strategy and the fact they were the first to release DRAM to heighten sales of the chips and create the success they did ( Lazonick 148-149). Intel’s business strategy was very aggressive and they knew how to play the market to maximize profits.

Need help to write reflection paragraph for my project about the Assignment

Need help to write reflection paragraph for my project about the strategy project on ( Cesim Business Management Simulations ) - Assignment Example We learned this during the course of the game. Sometimes, there just concepts that are too abstract for us to understand in a classroom setting and only appreciate it in a business setting. For example, we decided to make our costs and expense low in the last few rounds thinking that it would it increase our net profit by keeping the deductions down. Theoretically, our assumption should be right but it is just too simplistic to assume that net profit will increase if cost will be reduced because there are also other things to consider in making profit. In our case, we reduce our costs and expense to only 740,749 which is one of the lowest in the game. Theoretically, if our deductions were small, then our net profit should be high. We realize that it does not necessarily follow this way. Reducing costs, especially those that are critical in generating revenues is not always healthy for the business. We are also not efficient in using our resources to generate revenue. We may have one of the lowest costs in the game in terms of numbers but if we relate this to the revenue generated, we are in fact one of the costliest business if not the costliest. Now, this would be difficult to realize in a classroom discussion. We have a lot of fixed assets but it did not generate revenue and only incurred us depreciation of 437Â  722 which can be considered as the highest in the game even if it is not the highest in numbers term because it only generated a sales revenue of 1Â  273Â  665. These incorrect assumptions, led us to do poorly in the last few rounds of the game. We were doing great in the first few rounds but wrong assumptions pulled us in the read so to speak, in the last few rounds because we had wrong assumptions. Good thing this was just a game because if this was the real life, our team would have lost our shirt. The game served its purpose of letting us understand how various concepts and components in

Operations & Logistics Management Essay Example | Topics and Well Written Essays - 2250 words

Operations & Logistics Management - Essay Example Despite the fact that ISO standards are developed with the government support, certification on ISO 9000 is a completely voluntary matter. Pressure, constraining enterprise to carry out a certification, occur by users, but not legislative organs. Almost the most important fact, which is concerned this standard, is the fact that many companies, especially in Europe, require registration on ISO 9000 from their suppliers of goods and services. To cut the long story short we should say if there is no registration on ISO 9000 there is no concluded contract. In the USA, for example, NASA and Ministry of Defense now require certification on ISO 9000 from its suppliers. Let us consider the example of corporation DuPont, which is an example of enterprise, which corresponds to ISO. The activity of corporation is connected with world sales to the production of chemical industry. DuPont is one of the biggest chemical companies in the world. It was established in 1802 as manufacture for the production of powder. Nowadays DuPont produces a wide range of chemical products and conducts great innovational researches in this area. The company is an inventor of variety unique polymeric and other materials, such as neoprene, nylon, teflon, kevlar and other. The company was also developer and basic producer of the freon, utilized in the production of refrigerator devices. According to version of Fortune 500, the company occupies 66th place among the largest corporations of the USA. At present time DuPont is a multinational corporation that has 18 majo r businesses, operations in 70 countries and more than 60,000 employees. The gain of company in 2005 composed $26,6 billion. After the DuPont's certification in accordance with the requirements of the standards ISO 9000 it has began the stage of its implementation. Standards' implementation have not been so easy, since in comparison with the previous version (1994) serious changes underwent these standards, they now requires the reconsideration of approaches of management of quality and mastery of the new requirements, which are based on TQM philosophy and principles of the quality rewards models. Together with the unconditional progressiveness of the standards ISO 9000, especially new version, there is a potential danger of standards formal implementation. In the process of ISO standards implementation in DuPont there have appeared a range of complex problems, caused by the need of the systematic guarantee of realization of positions and requirements of these renovated standards, training of specialists and experts, and also by the lack of preparation of many certification organs for the work regarding c orrespondence of the systems of quality to new requirements.The main task, which have stood before the management of company was to avoid formal implementation into of ISO 9000 standards, since formal approach to this matter can bring only loss of time and expenses, and disappointment in standards themselves. Actually, under specific conditions ISO 9000 standards can not only prove to be

What is the essence of philosophy Essay Example | Topics and Well Written Essays - 750 words

What is the essence of philosophy - Essay Example n order to define what the essence of philosophy really is, I decided to examine the range of philosophers and philosophies that we have covered in class. In Chinese history there are tales of philosophers who placed an emphasis on finding a way of living a good life, which suggests that philosophy has to do with morality and self-control and this is very similar to some of the moral philosophy as taught by the ancient Greek philosopher Socrates. It is also similar to some of the teachings in the major world religions which see human life as a journey towards enlightenment or a preparation for an afterlife. This contrasts very strongly with some of the medieval European philosophers who emphasized the use of reason, and the power of thinking through issues using logical trains of thought. In the twentieth century there has been a considerable emphasis on language and on existential problems like the meaning of human life. In the twenty first century there is a growing realisation of the fragile nature of the planet earth and the need for human beings to find ways of living that are in harmony with nature, rather than just pursuing mat erialist aims, and disregarding or even destroying the environment around them. The most noticeable feature of philosophy appears to be its diversity. It changes from place to place and from one time period to the next. All of these different approaches can be called philosophy and one way of defining the essence of philosophy is to establish what it is that they all have in common. I think that asking questions is a fundamental part of philosophy, and then weighing up the answers that are found in such a way that new questions are asked and a continuous process of asking, answering, reflecting and asking again then follows. This is not exactly the same as the kind of questions that are asked by scientists, who are mostly interested in how the elements in the world behave and what rules exist in the universe. Philosophy explores

The role of emotion in racial prejudice Essay Example for Free

The role of emotion in racial prejudice Essay Racial prejudice was defined by Allport , one of the first researchers in psychology to investigate the issue, as an aversive or hostile attitude towards a person who belongs to a group, simply because he or she belongs to that group, and is therefore presumed to have the objectionable qualities ascribed to that group. It is an antipathy based on a faulty and inflexible generalization (Allport, 1954). Racial prejudice exists on 3 levels: behavioral, cognitive and affective. The actual discrimination or unequal treatment towards a particular group based on their race is the behavioral component of racial prejudice. The cognitive component is made up of stereotypes. Stereotypes are categories of cognitions concerning the members of a particular group. These cognitions are usually simple, often over generalized, and frequently inaccurate. Stereotypes are not simply abstractions about group categories. They can act as cognitive filters through which we select what information to use, what to ignore, and how to interpret it. Stereotypes do not exist in isolation. They are accompanied by emotions, which are usually expressed in terms that can be distributed along a continuum ranging from the intensely negative to the very positive. (Simpson and Yinger, 1972) The emotional level is a major element of racism, because it serves as the motivation for stereotyping. Stereotypes would not be so powerful without affective links. After the cognitive level has been challenged and undermined, one continues to maintain stereotypes at the emotional or affective level. As the intensity of emotion increases, so does the level of prejudice. This paper will explore the influence of emotions on ones unconscious and conscious inclinations towards stereotyping and racism. Fear, anxiety, disgust and anger are all emotions that exist at the root of racism. According to an evolutionary perspective, fear is one of the most motivational emotions humans have in their bodies to keep them alive. It protects humans from danger, by motivating them to fight back when they are being threatened. This fight manifests itself in many different ways, but in the context of racism it is in the form of discrimination towards an out-group. This explains racism as a means of fighting back when an individuals fear has been aroused due to perceived threat to an ones fundamental needs by the out-group. Fear exists in the reptilian brain, the very basic area of the brain and it can sometimes be aroused unconsciously. Fear can cause neurotransmitters to fill the brain, bringing an individual to such a heightened state of arousal that the cause of fear becomes internalized. (Le Doux, 2002) In the context of racism, if an individual or group is identified with that arousal, an association is made that is not easily removed. This evolutionary logic leads to many thoughts about factors in modern day society leading to the acquisition of new stereotypes and prejudices, as well as the endurance existing stereotypes and prejudices. For example, a recent study conducted by Schaller, Park and Mueller investigated the effect of ambient darkness and thoughts about danger on stereotypes about Blacks. The participants were placed in either a well lit or dark room, then they were presented photographs of black males and asked to rate how much they represented the cultural stereotype. The study also included a separate questionnaire to assess each participants thoughts of living in a dangerous world. The results showed that when the participants were in the well lit room, their level of perceived danger in the world did not have an effect on the intensity of their stereotypes of blacks. However, when the participants were in the dark room, stereotypes of blacks were more intense in association with their level of perceived danger in the world. To people everywhere darkness is a threat, it presents danger due to vulnerability and has evil connotations. This study clearly illustrates the relationship between racism and fear. (Schaller, Park Mueller, 2002). Inter-group anxiety has been proven to be another motivator for racial prejudice. High levels of intergroup anxiety may amplify normative behavioral patterns, cause cognitive and motivational information processing biases, intensify self-awareness, and augment emotional reactions (Stephan Stephan, 1985). Stephan and Stephan proposed that intergroup anxiety stems mainly from the anticipation of negative consequences for oneself during contact. Much of the intergroup anxiety may be caused by minimal previous contact with the outgroup, the existence of large status differentials, and a high ratio of outgroup to ingroup members. Stephan and Stephans own study of Hispanic Americans perceptions of Anglos showed that high voluntary contact was negatively associated, and that high believed dissimilarity and stereotyping were positively associated, with intergroup anxiety. It was predicted that increased contact (under appropriate conditions) would be associated with decreased intergroup anxiety and that, in the context of our field study of minority and majority religious groups, intergroup anxiety would be higher for minority group members. (Stephan Stephan, 1985) The Social-identity theory is widely used as an explanation for prejudice. According to Social-Identity theory, an individual attains self-concept and self-esteem through membership to a particular group. A high need for esteem and belonging are often associated with racism because of the psychological need it fulfill it to feel superior, (which in actuality is a state of inferiority). In order for individuals to feel as though their group is meaningful and has status, it is unconsciously necessary for them to place others below them. In applying emotion to this model of prejudice, it is evident that fear of rejection acts as a motivator for out-group discrimination in order to protect ones own ego. A newer model of prejudice; Intergroup Emotions Theory, combines this social identity perspective with the assumptions of appraisal theories of emotion. Intergroup Emotions Theory claims that emotions are caused by the collective aspect of the self. For example, when an outgroup is appraised as threatening an ingroup, negative intergroup emotions such as fear or anger may result, and become part of a general prejudice against the outgroup that may motivate discriminatory behavior. Thus, Intergroup Emotions Theory holds that emotions experienced by individuals with respect to their group memberships make a unique contribution to prejudice and intergroup relations. In association with the Intergroup Emotion Theory which recognizes the appraisals and attribution process in racial motives. Esses, Haddock and Zanna point out that there is more to prejudice than merely the attribution of stereotypes to groups. Their research suggests that the emotions elicited by a particular group are important in determining ones level of prejudice. When one is in a good mood, he or she is likely to evaluate members of out-groups more favorably than when he or she is in a bad mood. (Esses, Haddock Zanna, 1993) Another example of the role emotion plays in predicting racial prejudice is illustrated in a study by Esses and Dovidio. They found that when white students were shown a videotape of a black man experiencing discrimination in several situations and asked to focus on their feelings about each situation, they felt more positive toward blacks and were more willing to interact with blacks in the future than students who were told to pay attention to their thoughts in this regard. Aversive racism is yet another way in which emotion is seen as a factor in racism. Aversive racism is accompanied by feelings of anxiety, which are caused by intergroup expectancies and by the contribution of ignorance that often coexists with fear. Gaertner and Dovidio state that aversive racism is excluded from conscious awareness and amplifies positive behaviours toward a minority group. Negative feelings follow these overly positive behaviours. Gaertner and Dovidio indicate that there are several possible negative emotions involved such as discomfort, anxiety, uneasiness, disgust and even fear. These emotions occur because of the extreme cognitive exercise necessary to avoid expressing unacceptable racist comments. Once again it is being suggested that negative emotions mediate the relationship between stereotypes, which are unavoidable, and prejudice that includes affect. (Gaertner and Dovidio, 1986) The studies mentioned throughout this paper prove that emotions play a significant role in human tendencies towards racial prejudices. It is also evident that these tendencies can be in many ways unconscious. However, much of this research has also shown that if humans are made more aware of the role that their emotions play in these prejudice thoughts and actions, they can learn to monitor them consciously. Also other research has noted that by increasing intergroup contact racism between groups will decrease. Racial prejudice is a major social problem that must be alleviated and more research in this area will always be beneficial in helping society become more unified. Works Cited Allport, The Nature of Prejudice, Doubleday, 1958 Esses, V. Dovidio, J. (2002). The role of emotions in determining willingness to engage in intergroup contact. Personality and Social Psychology Bulletin, 29, 637-649. Esses, V. M. , Haddock, G. , Zanna, M. P. (1993). Values, stereotypes, and emotions as determinants of intergroup attitudes. In D. M. Mackie D. L. Hamilton (Eds. ), Affect, cognition and stereotyping: Interactive processes in group perception (pp. 137-166). San Diego: Academic Press. Gaertner, S. L. , Dovidio, J. F. (1986). The aversive form of racism. In J. F. Dovidio S. L. Gaertner (Eds. ), Prejudice, Discrimination, and Racism. Orlando, FL: Academic Press. LeDoux, Joseph. The Synaptic Self: How Our Brains Become Who We Are. Viking, 2002. Schaller, M. , Park, J. , Mueller, A. (2002). Fear of the dark: Interactive effects of beliefs about dander and ambient darkness on ethnic stereotypes. Personality and Social Bulletin, 28, 1242-1254. Simpson G. E. Yinger J. M, Racial and Cultural Minorities. An Analysis of Prejudice and Discrimination, New York 1972, p. 24. Stephan, W. G. , Stephan, C. W. (1985). Intergroup anxiety. Journal of Social Issues, 41(3), 157-175.

Multifunctional Porous Organics Synthesis

Multifunctional Porous Organics Synthesis TITLE OF WORK The synthesis and characterisation of functionalized porous organics Abstract Lophine based radicals have been studied for many years due to their photochromic nature, recent literature has seen attempts to connect two radicals to carbon based backbones. In this report we will discuss attaching six lophine molecules to a single backbone which is a phosphazene ring. Cyclophosphazene rings have a unique conformation allowing for supramolecular architectures to be formed by varying the substituents, these architectures range from 0-2D structures. The hexalophine molecule exhibits 1D channels due its unique conformation which leads to the formation of a porous material. Porous organics are of high interest in recent literature due to them being a cheaper, less toxic alternative to MOFs as well as having the ability to be modified and tailored easily due to the simple starting materials. In this report we shall state synthetic pathways from simple molecular building blocks to hexalophine (32%) and two derivatives, compound 4 (46%) and 5 (15%). These two derivatives have the potential to increase pore stability. This report will also include the oxidation of hexalophine to its radical species which were found to display photochromic properties and it is also believed that this material could contain light gated pores which are closed in the dimer form of the product but then open upon irradiation of UV of 365nm. 1. INTRODUCTION 1.0 Properties and potential uses of Lophine This report will feature chemistry based upon the triphenylimidazolyl based radicals (TPIRs) as well as the dimer form hexaarylbiimidazole (HABI). Lophine (2,4,5-triphenyl-1H-imidazole) is a heterocyclic imidazole derivative where three phenyl rings are attached to the imidazole ring (figure 1), these imidazole derivatives are an area of importance due to the many interesting properties it possesses. Lophine has been of interest to researchers for many years with its chemiluminescent properties being first discovered in 1877 by Radziszewski.1 The oxidation of the lophine molecule follows the reaction scheme below, where lophine is oxidised to the TPIR radical state via addion of base and treatment with Fe forming one of six dimers both in solution and the solid state (figure 2). These materials display photochromic, thermochromic and piezochromic properties. The mechanism of photochromism of the lophine dimer is the homolytic cleavage of the 2C-1N bond of the dimer by irradiation wit h light, forming two lophine radicals.2 The fast colour change associated with this dimer opening means there is a potential use in display screens or as the basis for molecular switches, where irradiation with light opens the dimer forming the radical in turn switching the external component On/Off. These possible applications have caused a focus on creating methods to manipulate and control the colour of these materials and as well as to increase the rate of switching.3 The colour of the radical form is dependent upon the substituents on the ring, the more conjugated the system the further toward the red side of the spectrum the colour.4 Lophine displays piezochromic properties in its solid state, upon applying pressure lophine crystals the colour change of yellow to blue/green has been observed, this occurs via the radical dissociation of the 1N-1N dimer bond.5 Other more unusual modes have been of dimerization such as the 2C-2C have now also been isolated, this mode features a u nusually long C-C bond.3 Figure 1 The structure of Lophine (2,4,5-triphenyl-1H-imidazole) Another interesting lophyl radical derivative is the 1,8-TPID-naphthalene radical which consists of 2 lophine radicals connected by a naphthalene ring. 1,8-TPID-naphthalene has been characterised in the solid state by Abe et al; who studied the photoreactivity of the compound. 1,8-TPID-naphthalene allowed the group to fix two radicals onto a backbone meaning that the radicals were in close proximity and could dimerise easily as opposed to two radicals not connected via a backbone which first need to find eachother in order for dimerization to occur (figure 3). They found that the dimer could be cleaved photochemically giving the diradical and then could be thermally converted back to the dimer.6 They also found that the formation of a peroxide bridge was much more common than previous literature had accounted for. This bridging occurred when the 1,8-TPID-naphthalene radical was placed under an O2 atmosphere.7 This peroxide bridge formation is very important as when oxygen quenches th e spin to form the closed shell peroxide it does so irreversibly meaning the material is no longer photochromic. It was then shown that this peroxide degradation pathway can be generalised for the chromic dimers of TPIR materials, with non-tethered TPIRs forming similar peroxide bridges.8 A recent development by the same research group has also shown how a thiophene substituted phenoxyl-imidazole radical complex (PIC) can generate two non-equivalent radical upon irradiation with UV light. The colour change can be fine-tuned from tens of seconds to nanoseconds, however a sensitivity to lower wavelengths of light meant that applications were limited. This problem was rectified by adding a phenyl group to the 5 position of the thiophene ring.9 Figure 2 The six potential dimerization modes of two lophyl radicals.3 Figure 3 Illustrates the reversible conversion of 1,8-TPID-naphthalene between its radical and dimer forms. 1.1 Hexa-substituted Phophazene Rings, Tectons and Crystal Engineering A key component of this project was the exploitation of the Phosphazene ring as soft tecton; a tecton is a molecular building block that interacts with sticky sites, formally known as supramolecular synthons, via spatial arrangements to induce the formation of supramolecular aggregates. The search for new tectons is a hot area of research due to the constantly growing field of crystal engineering where the aim is to produce functional single crystal materials using intermolecular interactions. The arrangement of molecules in solid state structures is largely dependent on striking a fine balance between intramolecular forces and packing interactions, knowledge of these forces is key to the field of crystal engineering.10 In general, hard tectons interact via more robust synthons than soft tectons and therefore usually crystallise with unambiguous geometries. Whereas soft tectons and less robust synthons allow for the formation of supramolecular isomers (figure 4).11 These tectons allo w for many functional materials to be formed in a one pot synthesis, they also have the ability to be carefully adjusted to alter and improve upon their functionality.12 Cyclophosphazenes are extremely soft tectons that interact with soft synthons to give a large variety of supramolecular architectures in the solid state. The conformation of the cyclophosphazenes is also very interesting as three substituents reside above the plane of the ring and three below (figure 5). It was found that small modifications to the substituents attached to the ring gave supramolecular architectures ranging from 0D to 2D structures (figure 6) such as include monomer, dimer, cyclic hexamer, zigzag chain, linear chain, double chain, graphite-type sheet, rectangular grid and hexagonal close-packed sheet. Such variety of structures came from the easy rotation about the exocyclic P-N bonds, which allowed variable directionalities for all of the N-H bonds. 11   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   3a)  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   3b) Figure 4a) Shows benzene-1,4-dicarboxylic acid a classic example of a hard tecton. 4b) shows a silanetriol a classic soft tecton. Figure 5 Conformation of a Hexa-substituted Phosphazene Ring. Figure 6 Schematic representations of aggregation patterns of (RNH)6P3N3 in the solid state.11 1.2 Magnetism and Magnetic Frustration The materials we aim to make during this project once appropriately oxidised should go on to form dimers which when irradiated with UV light form discrete radicals containing unpaired electrons thus giving each radical an associated magnetic moment. Neutral organic radicals tend to be paramagnetic and exhibit Curie- Weiss behaviour, where the spin vectors of the unpaired electrons are randomly aligned above the Curie temperature (Tc), which is the critical temperature below which the long ordered state is established, unless a magnetic field is applied. If spin vectors are parallel to each other below the Curie temperature then the material is ferromagnetic, if the spin vectors are aligned antiparallel to one another the material is antiferromagnetic.13 Due to the geometry of the phosphazene ring (three substituents pointing up above the plane of the ring and three below) there is the possibility of forming a 2D triangular lattice of spins if the substituents are organic radicals.   This could possibly lead to geometric magnetic frustration due to the fact that the two nearest neighbours to a spin are themselves nearest neighbours and therefore antiferromagnetic couplings cannot be satisfied (figure 7).14 This can lead to very interesting magnetic properties. Most solid state examples of this geometric frustration tend to be transition metal oxides, however, studies have been done on organic systems that also distribute geometric frustration.13 One example of this is m-MPYNNP+ which is a spin  ½ organic radical that upon dimerization forms a 2D triangular lattice which demonstrates the aforementioned geometric frustration.14 The issue of spin frustration has been around for a long time as Quantum spin liquids (QSL) were first theoretically proposed by Anderson many years ago which are now a hot topic of research due to the realisation of these QSLs in organic materials such as k-(ET)2-CH2(CN)3, which has a near perfect triangular lattice with angles very close to 120 °.15 A QSL is an exotic ground state where interacting spins continuously fluctuate with no formation of   low range magnetic order even at sufficiently low temperatures.16 Figure 7 Antiferromagnetic coupling cannot be fulfilled causing geometric magnetic frustration. 1.3 Porous Materials Porous materials are as important as ever due to their wide spread use in several fields such as catalysis and gas absorption,17 meaning they can play a critical role in the route to solving our growing energy shortage problems. Porous materials are instantly associated with materials such as zeolites, metal organic framework (MOF) and organic polymers. MOFs are characterised by their tuneable pores and inherent flexibility which more classical carbon or oxide based structures do not possess, this gives a wide range of applications for MOFs such as gas storage, separation, drug delivery or catalysis.18 Porous organics have been discovered in nature but are largely created synthetically and approaches often need to be coupled with knowledge of crystal engineering. These materials are often held together by directional forces which form extended frameworks of noncovalent interactions such as Ï€- Ï€ interactions, hydrogen bonding or coordinate bonding (figure 8).17 Like zeolites a nd MOFs porous organics have the ability to selectively absorb atoms and molecules in the gas phase.19 There are many positives to these porous organics, they are often cheaper to synthesise and less toxic as well as being far less dense than metal containing MOFs. Figure 8 One example of a Porous Organic by Sozzani et al. 1.4 P3N3 Hexalophine The chemistry of P3N3 Hexalophine incorporates much of the chemistry discussed above and has many interesting properties. The P3N3 Hexalophine molecule consists of six lophine substituents attached to the phosphazene ring via a P-O bond (figure 9). Previous work in the Robertson group found that the solid state structure of Hexalophine consisted of a pseudo hexagonal motif giving rise to 1D channels that run parallel to the stacking axis (figure 10). The molecule maintained its D3 symmetry in the solid state. The phenyl rings twist to maximise pi-stacking interaction and the 3 imidazole nitrogen atoms form hydrogen bonds to a central water molecule. There are 4 pi-pi interactions that stabilise this structure, the molecules are in a slipped conformation allowing the phenyl and imidazole to rings overlap. Other non-covalent interactions such as van der Waals interactions also help to stabilise the structure. The high symmetry of the structure which comes from the hexa substituted phos phazene ring (three above the plane of the ring and three below) gives an equal distribution of intermolecular forces giving a high probability of forming a stable porous structure. IGA measurements with CO2 loading at 195K shows a Type I isotherm with absorption reaching 8cm3g-1 at a pressure of 700mmHg confirming the materials microporosity. However only a small fraction of the void space contained CO2. Figure 9 The structure of Hexalophine. Figure 10 The crystal structure of Hexalophine, illustrating the 1D channels. 1.5 Aim of Project The aim of this project is to combine our knowledge of the chemistry of both lophine radical systems and cyclophosphazene rings to find elegant synthetic routes which will improve upon the porous properties of hexalophine. This will be done by varying the ring substituents to increase stability of the pores and to improve its gas absorption properties. Three lophine derivatives have been identified as plausible candidates for thid are where two of the phenyl groups on the lophine will be replaced by two thiophene rings and two pyridine rings respectively, with the position of the nitrogen in the pyridine ring being varied depending upon the synthetic pathway (figure 11). We wish to synthesise and fully characterise these derivatives including growing single crystals for structural studies via X-ray crystallography. Also a stoichiometric controlled oxidation of the hexalophine material to its neutral radical/dimer pair is required in order to further investigate the properties of hexa lophine such as the possibility of creating a photochromic material that has light gated pores that open on irradiation with UV light. R=  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   or  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   or Figure 11 the synthetic targets of this project. 2. Results and discussion 2.0 Hexa-benzaldehyde Synthesis The first step in this synthetic project involved attaching six benzaldehyde units to the phosphazene ring via a P-O oxygen bond. This was achieved by reacting the phosphonitrillic chloride trimer along with 6 equivalents of 4-hydroxybenzaldehyde, potassium carbonate in dry THF (figure 12). The reaction was monitored with 31P NMR which showed completion when only a singlet was present in the spectra indicating full substitution. This produced the compound 1 which was the precursor for many of the subsequent reactions. The reaction gave the desired product in a fairly low yield (45%). Whilst the yield was slightly low the FT-IR showed all of the characteristic absorptions such as C=O (1697cm-1) and CAr-CAr (1585cm-1). 31P NMR was conducted and showed a sharp singlet at 7.08ppm which indicated full substitution on the phosphazene ring as all of the environments are equivalent. 1H NMR was also conducted and show a singlet at 9.87ppm with an integration of 6Hs which was as expected for t he 6 aldehyde protons, two doublets were found in the aromatic region and integrated to 12Hs each which was correct for the number of protons expected. The CHN analysis was almost perfect with less than 0.2% difference from the calculated values, this indicated that the product was of high purity. Mass spectometry also indicated that the desired product had been synthesized as a [M+Na]+ peak was detected at 884. Figure 12 The reaction scheme for the synthesis of 1. 2.1 Synthesis of Hexalophine and Hexalophine derivatives 2.1.0 Using Diketones The synthesis of hexalophine and hexalophine derivatives is important due to their porous properties which can be of great importance in fields such as gas storage and catalysis. The method for attaching six lophine units to the ring was a ring condensation of 1 on the six benzaldehyde units attached to the phosphazene ring using a synthesis based upon Radziszewskis synthesis.1 The product 2 was achieved by reacting 1 along with six equivalents of benzil, ammonium acetate in excess in glacial acetic acid (figure 13). The yield for 2 was quite poor (32%), the FT-IR showed all of the characteristic peaks such as CAr-H (3055cm-1), C=N (1604cm-1) and CAr=CAr (1538cm-1) indicating the desired product had been formed. This was further confirmed by both the 31P and 1H NMR, the 31P NMR showed a singlet at 8.36ppm which indicates full substitution on the phosphazene ring. The 1H NMR showed a singlet at 12.65ppm which had an integration equal to 6Hs which is representative of the 6 imidazole N -Hs, it also showed multiplets in the aromatic region with an integration of 84Hs which is exactly the number of aromatic hydrogens in the desired product. CHN analysis of the product correlated well with the desired structure, especially when three molecules of water were factored into the calculation. It is unsurprising that this compound also contained water due to its porous nature.   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   NH4OAc   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Acetic acid (6eq.) Figure 13 The reaction scheme for the synthesis of 2. Another reaction designed based upon the ring condensation reaction was the synthesis of 4. This synthesis builds upon the diketone functionality as above, however, in this reaction the R groups of the diketone thenil were thiophene rings as opposed to the phenyl rings of benzil. Thenil like benzil was reacted with 1 and ammonium acetate in glacial acetic acid (figure 14). The yield for this compound, whilst better than 2, was still fairly low (46%). FT-IR showed the characteristic peaks such as CAr-H (3071cm-1), CAr=CAr (1643cm-1) and C=N (1607cm-1) indicating the target molecule had been synthesised. The 31P NMR showed a singlet at 8.26ppm again indicating full substitution. The 1H NMR showed a singlet 12.91ppm with an integration of 6Hs representative of the 6 imidazole N-H hydrogens, it also showed multiplets in the aromatic region with an integration of 60 which was again exactly what was required for the number of aromatic hydrogens, indicating the correct product had been synt hesised. The CHN analysis was close to the theorectical values required especially when four water molecules were factored in, again this is unsurprising as this material like 2 is also expected to be porous.   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   NH4OAc   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Acetic acid (6eq.) Figure 14 The reaction scheme for the synthesis of 4. Like thenil and benzil, pyridil is also a diketone where the two R groups are heterocycles, in this case the two heterocycles are pyridine rings. Pyridil was used again with the classical Radziszewski based synthesis to synthesise the compound 5 (Figure 15). The yield for this compound was very low (15%) due to a lot of mass lost upon recrystallization and decomposition upon heating. The FT-IR showed the correct absorptions for the key functional groups such as C=N (1600cm-1) and P=N (1158cm-1) indicating that the target compound had been synthesised. However large OH absorption band (3349cm-1) was also present showing that the product contained a considerable amount of water or ethanol. CHN analysis of the compound showed a vast difference in carbon and nitrogen values when compared to the theoretical values indicating some impurities in the sample. The fact that the product contained considerable amounts solvent would also skew the result of the CHN analysis somewhat.   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   NH4OAc   Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚  Ã‚   Acetic acid (6eq.) Figure 15 The reaction scheme for the synthesis of 5. 2.1.1 Using Aldehydes for an alternative preparation The idea of using aldehydes such as pyridine carboxyaldehyde and benzaldehyde as opposed to the diketones used above was born when questioning on how we could stabilise the pores in the materials we wished to synthesise as larger groups could be added to these aldehyde starting materials. An alternative synthesis of 2 using twelve equivalents of benzaldehyde is illustrated in figure 16. The reaction was left to reflux for 7 days however the 31P NMR showed a multiplet indicating that full substitution had not occurred or a mix of products was present. Unfortunately, this was a reoccurring theme as the failed synthesis of 3 using twelve equivalents of pyridine carboxyaldehyde (figure 17) also showed a multiplet in the 31P NMR. Benzaldehyde (12 eq.) Figure 16 The reaction scheme for and alternative preparation of 2. Carboxyaldehyde (12 eq.) Figure 17 The reaction scheme for compound 3. 2.2 Oxidation of Hexalophine and its derivatives The oxidation of hexalophine is of great interest due to the potential properties it may possess, such as it possessing photochromic properties which may lead to light gated pores. For this oxidation an excess of potassium hydroxide was used to create the anion before 50 equivalents of the classical oxidising agent potassium ferrocyanide (III) were used to perform a one electron oxidation to the radical species 6, a yellow to orange colour change is associated with the formation of the radical species. This radical species quickly dimerises and an orange to yellow colour change is associated with this. Upon irradiation with UV light (365nm) the dimer opens to form two radicals, the colour change associated with this was yellow to purple displaying the photochromic behaviour of this compound (figure 18). The radical species is stable for a number of hours in the solid state unless gentle heating is applied which induces dimerization again and the colour change of purple to yellow is a ssociated with this. FT-IR showed characteristic absorbances of CAr-H (2955cm-1), C-N (1301cm-1) and P=N (1198cm-1) which are present in the desired product. The thiophene hexalophine derivative 4 was also oxidised using the same classical oxidation conditions as above to form its radical species 7. Upon separation the system formed 3 layers, an organic layer, an aqueous layer and a solid substance formed which was soluble in neither. Both the organic layer and solid substance were irradiated with UV light to test for photochromic properties however neither displayed a colour change and thus further testing of this material via UV/Vis spectroscopy is required to determine its nature. Figure 18 A RBF containing the hexalophine dimer and radical, the purple is the radical species, the yellow is the dimer species. 3. Conclusions and further work The aim of this project was to synthesise and characterise functionalised porous organics based upon hexalophine as well as to perform oxidations to the radical species and study their properties such as photochromism. For the most part the aim of the project has been met as two derivatives of hexalophine (4 and 5) and hexalophine (2) itself have been synthesised from simple molecular building blocks and characterised using a range of spectroscopic techniques such as NMR, FT-IR and CHN analysis. The next step in the characterisation of these materials would be to gain crystal structures via x-ray crystallography to show the packing arrangement of these molecules and to prove the existence of pores with in the molecule created from the unique conformation of the phosphazene ring. Additionally, once crystal structures have been gained gas absorption test should be taken to test both the gas uptake properties and selectivity of certain gases. Yields for these experiments were quite low and the aldehyde reactions did not demonstrate full substitution onto the ring, one possible solution would be to try the reaction in a Parr pressure reactor. The oxidation of hexalophine was carried out with great success as the experiment demonstrated the proposed photochromic nature of the material, also the stability of this material with respect to air was very surprising. If possible crystal structures for this material should be obtained in order to investigate further the possibility of light gated pores which when the molecule is in the dimer form are closed but once in the radical form are open. 4. Experimental details 4.0 Ma