1. Nickel 1,4-cyclohexanedicarboxylate coordination polymers – Synthesis, Characterization, Phase study, and Magnetic Properties Prashant Jain @, Russel K Feller #, Naresh Dalal @, Tony Cheetham #, and Harold W. Kroto @ @ Dept. of Chemistry & Biochemistry, Florida State University, # Materials Research Laboratory, University of California, Santa Barbara Overview Coordination polymers or metal organic frameworks are of great recent research interest due to their interesting topologies and potential applications as functional materials. Hydrothermal chemistry has been widely used for preparation of these compounds. Control of products in the hydrothermal reactions is still an exciting challenge for the chemists. Here we report the synthesis of five nickel complexes starting from identical reaction mixture. A detailed study was conducted to determine the way in which reaction conditions governed the resulting phases. Temperature and concentration were found to be the two main determining factors. Products Five nickel complexes were observed. Structures of three complexes were solved by single crystal XRD. For complex 4 (space group R3-c) the temperature dependence of reciprocal of the susceptibility is linear above 60 K and obeys the Curie-Weiss law with a Weiss constant θ = - 146.89 K and C = 9.43 cm 3 K mol -1. The C value correspond to the six non-interacting Ni II ions (S=1) with g = 2.21. χT value at room temperature (6.33 cm 3 K mol -1 ) is lower then an expected value (7.33 cm 3 K mol -1 ). Effect of reaction conditions As shown in the reaction condition diagram, it was possible to synthesize pure complexes. Other variables (eg. solvent volume, fill volume, stirring etc.) do not affect the products though they have an effect on crystal size. Compound 4 has a unique structure with hexanuclear nickel cluster forming 2-D layers. Magnetic measurement for 4, suggest that there are competing ferromagnetic and anti-ferromagnetic behavior with complex being anti-ferromagnetic at lower temperatures. Reaction time was reduced to less then 2 hours in microwave synthesis with higher yield. Magnetic studies are underway to understand interactions within these complexes. Observations [Ni 6 (OH) 6 (trans-1,4-CHDC) 3 (H 2 O) 6 ].2H 2 O Space Group: R3-c [Ni 3 (OH) 2 (trans-1,4-CHDC) 2 (H 2 O) 4 ].4H 2 O Space Group: C2/m [Ni 3 (OH) 2 (cis-1,4-CHDC) 2 (H 2 O) 4 ].2H 2 O Space Group: P2 1 /c Crystal Structures Magnetic Measurements X-ray Diffraction Data Synthesis Products were characterized by single crystal and powder XRD. NiAc + CHDC (Hydrothermal reaction for 2 Days) Nickel 1,4 cyclohexanedicarboxylate

2. Nickel 1,4-cyclohexanedicarboxylate coordination polymers – Prashant Jain @, Russel K Feller #, Naresh Dalal @, Tony Cheetham #, and Harold W. Kroto @ @ Dept. of Chemistry & Biochemistry, Florida State University, # Materials Research Laboratory, University of California, Santa Barbara Synthesis, Characterization, Phase study, and Magnetic Properties

3. Coordination polymers or metal organic frameworks (MOFs) have very interesting topologies and important potential applications as functional materials.

4. Nickel 1,4-cyclohexanedicarboxylate

5. Ni 6 (OH) 6 (chdcox) 3 (H 2 O) 6.2H 2 O

8. Nickel 1,4-cyclohexanedicarboxylate coordination polymers – Synthesis, Characterization, Phase study, and Magnetic Properties Prashant Jain @, Russel K Feller #, Naresh Dalal @, Tony Cheetham #, and Harold W. Kroto @ @ Dept. of Chemistry & Biochemistry, Florida State University, # Materials Research Laboratory, University of California, Santa Barbara Overview Coordination polymers or metal organic frameworks are of great recent research interest due to their interesting topologies and potential applications as functional materials. Hydrothermal chemistry has been widely used for preparation of these compounds. Control of products in the hydrothermal reactions is still an exciting challenge for the chemists. Here we report the synthesis of five nickel complexes starting from identical reaction mixture. A detailed study was conducted to determine the way in which reaction conditions governed the resulting phases. Temperature and concentration were found to be the two main determining factors. Products Five nickel complexes were observed. Structures of three complexes were solved by single crystal XRD. For complex 4 (space group R3-c) the temperature dependence of reciprocal of the susceptibility is linear above 60 K and obeys the Curie-Weiss law with a Weiss constant θ = - 146.89 K and C = 9.43 cm 3 K mol -1. The C value correspond to the six non-interacting Ni II ions (S=1) with g = 2.21. χT value at room temperature (6.33 cm 3 K mol -1 ) is lower then an expected value (7.33 cm 3 K mol -1 ). Effect of reaction conditions As shown in the reaction condition diagram, it was possible to synthesize pure complexes. Other variables (eg. solvent volume, fill volume, stirring etc.) do not affect the products though they have an effect on crystal size. Compound 4 has a unique structure with hexanuclear nickel cluster forming 2-D layers. Magnetic measurement for 4, suggest that there are competing ferromagnetic and anti-ferromagnetic behavior with complex being anti-ferromagnetic at lower temperatures. Reaction time was reduced to less then 2 hours in microwave synthesis with higher yield. Magnetic studies are underway to understand interactions within these complexes. Observations [Ni 6 (OH) 6 (trans-1,4-CHDC) 3 (H 2 O) 6 ].2H 2 O Space Group: R3-c [Ni 3 (OH) 2 (trans-1,4-CHDC) 2 (H 2 O) 4 ].4H 2 O Space Group: C2/m [Ni 3 (OH) 2 (cis-1,4-CHDC) 2 (H 2 O) 4 ].2H 2 O Space Group: P2 1 /c Crystal Structures Magnetic Measurements X-ray Diffraction Data Synthesis Products were characterized by single crystal and powder XRD. NiAc + CHDC (Hydrothermal reaction for 2 Days) Nickel 1,4 cyclohexanedicarboxylate

9. The temperature dependence of reciprocal of the susceptibility is linear above 60 K and obeys the Curie-Weiss law

12. → 1/χM1/χM

13. The temperature dependence of reciprocal of the susceptibility is linear above 60 K and obeys the Curie-Weiss law with a Weiss constant θ = - 146.89 K and C = 9.43 cm3 K mol-1.

14. → 1/χM1/χM

17. Functional materials are an essential part of our everyday lives. 1.silicon chip with its ever-increasing power 2.light-emitting materials at the heart of today’s telecommunications or DVD players 3.liquid crystal displays 4.magnetic materials used in recording devices.

18. For complex 4 (space group R3-c) the temperature dependence of reciprocal of the susceptibility is linear above 60 K and obeys the Curie-Weiss law with a Weiss constant θ = -146.89 K and C = 9.43 cm3 K mol-1. The C value correspond to the six non-interacting NiII ions (S=1) with g = 2.21. χT value at room temperature (6.33 cm3 K mol-1) is lower then an expected value (7.33 cm3 K mol-1).

19. Functional materials are an essential part of our everyday lives.

20. 1.silicon chip with its ever-increasing power

22. Functional materials are an essential part of our everyday lives. 1.silicon chip with its ever-increasing power 2.light-emitting materials at the heart of today’s telecommunications or DVD players

24. Functional materials are an essential part of our everyday lives. 1.silicon chip with its ever-increasing power 2.light-emitting materials at the heart of today’s telecommunications or DVD players 3.liquid crystal displays

26. Functional materials are an essential part of our everyday lives. 1.silicon chip with its ever-increasing power 2.light-emitting materials at the heart of today’s telecommunications or DVD players 3.liquid crystal displays 4.magnetic materials used in recording devices.

27. As shown in the reaction condition diagram, it was possible to synthesize pure complexes. Other variables (eg. solvent volume, fill volume, stirring etc.) do not affect the products though they have an effect on crystal size. Compound 4 has a unique structure with hexanuclear nickel cluster forming 2-D layers. Magnetic measurement for 4, suggest that there are competing ferromagnetic and anti-ferromagnetic behavior with complex being anti- ferromagnetic at lower temperatures. Reaction time was reduced to less then 2 hours in microwave synthesis with higher yield. Magnetic studies are underway to understand interactions within these complexes.

28. Functional materials are ubiquitous. New materials with improved functionality will be in demand in the marketplace and materials exhibiting more than one degree of functionality will appear to provide even more applications

29. 2 D oligomer self-assembly

31. Hydrothermal chemistry has been widely used for preparation of these compounds. Control of products in the hydrothermal reactions is still an exciting challenge for the chemists. Here we report the synthesis of five nickel complexes starting from identical reaction mixture.

34. Effect of reaction conditions

36. 100 125 150 175 200 Temperature

37. Effect of reaction conditions 100 125 150 175 200 Temperature

38. ©

39. © Pile of flat sheets

40. Nickel 1,4-cyclohexanedicarboxylate coordination polymers – Synthesis, Characterization, Phase study, and Magnetic Properties Prashant Jain @, Russel K Feller #, Naresh Dalal @, Tony Cheetham #, and Harold W. Kroto @ @ Dept. of Chemistry & Biochemistry, Florida State University, # Materials Research Laboratory, University of California, Santa Barbara Overview Coordination polymers or metal organic frameworks are of great recent research interest due to their interesting topologies and potential applications as functional materials. Hydrothermal chemistry has been widely used for preparation of these compounds. Control of products in the hydrothermal reactions is still an exciting challenge for the chemists. Here we report the synthesis of five nickel complexes starting from identical reaction mixture. A detailed study was conducted to determine the way in which reaction conditions governed the resulting phases. Temperature and concentration were found to be the two main determining factors. Products Five nickel complexes were observed. Structures of three complexes were solved by single crystal XRD. For complex 4 (space group R3-c) the temperature dependence of reciprocal of the susceptibility is linear above 60 K and obeys the Curie-Weiss law with a Weiss constant θ = - 146.89 K and C = 9.43 cm 3 K mol -1. The C value correspond to the six non-interacting Ni II ions (S=1) with g = 2.21. χT value at room temperature (6.33 cm 3 K mol -1 ) is lower then an expected value (7.33 cm 3 K mol -1 ). Effect of reaction conditions As shown in the reaction condition diagram, it was possible to synthesize pure complexes. Other variables (eg. solvent volume, fill volume, stirring etc.) do not affect the products though they have an effect on crystal size. Compound 4 has a unique structure with hexanuclear nickel cluster forming 2-D layers. Magnetic measurement for 4, suggest that there are competing ferromagnetic and anti-ferromagnetic behavior with complex being anti-ferromagnetic at lower temperatures. Reaction time was reduced to less then 2 hours in microwave synthesis with higher yield. Magnetic studies are underway to understand interactions within these complexes. Observations [Ni 6 (OH) 6 (trans-1,4-CHDC) 3 (H 2 O) 6 ].2H 2 O Space Group: R3-c [Ni 3 (OH) 2 (trans-1,4-CHDC) 2 (H 2 O) 4 ].4H 2 O Space Group: C2/m [Ni 3 (OH) 2 (cis-1,4-CHDC) 2 (H 2 O) 4 ].2H 2 O Space Group: P2 1 /c Crystal Structures Magnetic Measurements X-ray Diffraction Data Synthesis Products were characterized by single crystal and powder XRD. NiAc + CHDC (Hydrothermal reaction for 2 Days) Nickel 1,4 cyclohexanedicarboxylate

41. Functional materials are ubiquitous. New materials with improved functionality will be in demand in the marketplace and materials exhibiting more than one degree of functionality will appear to provide even more applications

43. As shown in the reaction condition diagram, it was possible to synthesize pure complexes. Other variables (eg. solvent volume, fill volume, stirring etc.) do not affect the products though they have an effect on crystal size. Compound 4 has a unique structure with hexanuclear nickel cluster forming 2-D layers. Magnetic measurement for 4, suggest that there are competing ferromagnetic and anti-ferromagnetic behavior with complex being anti-ferromagnetic at lower temperatures. Reaction time was reduced to less then 2 hours in microwave synthesis with higher yield. Magnetic studies are underway to understand interactions within these complexes. Observations

46. Hydrothermal chemistry has been widely used for preparation of these compounds. Control of products in the hydrothermal reactions is still an exciting challenge for the chemists. Here we report the synthesis of five nickel complexes starting from identical reaction mixture. A detailed study was conducted to determine the way in which reaction conditions governed the resulting phases. Temperature and concentration were found to be the two main determining factors.

47. Overview Coordination polymers or metal organic frameworks (MOFs) are of great recent research interest due to their interesting topologies and potential applications as functional materials. Hydrothermal chemistry has been widely used for preparation of these compounds. Control of products in the hydrothermal reactions is still an exciting challenge for the chemists. Here we report the synthesis of five nickel complexes starting from identical reaction mixture. A detailed study was conducted to determine the way in which reaction conditions governed the resulting phases. Temperature and concentration were found to be the two main determining factors.