We have prepared a series of N-picolyl-1,8-naphthalimide derivatives and explored their coordination chemistry with d-block metal ions in the solid and solution states,and exploited the structural and chemical propert...We have prepared a series of N-picolyl-1,8-naphthalimide derivatives and explored their coordination chemistry with d-block metal ions in the solid and solution states,and exploited the structural and chemical properties of these ligands to generate a family of robust metallogels.The 2-picolyl substituted ligands N-(2-picolyl)-1,8-naphthalimide L1 and N-(2-picolyl)-4-nitro-1,8-naphthalimide L2 showed interesting coordination behaviour in Mn,Co and Zn complexes 1-5,chelating through the pyridyl nitrogen atom and naphthalimide oxygen atom with subsequent bond localisation in the imide ring,the first example of such coordination behaviour to be structurally characterised.The 3-picolyl substituted ligands N-(3-picolyl)-1,8-naphthalimide L3 and N-(3-picolyl)-4-nitro-1,8-naphthalimide L4 vary in their coordination behaviour;the 4-unsubstituted ligand L3 acts as a simple monodentate donor giving crystalline assemblies,while the 4-nitro analogue L4 instead forms robust metallogels on reaction with Mn^(II) or Co^(II).The gels were found to be thermally and chemically reversible under various stimuli,and similar materials could be generated by installing a piperidinyl substituent at the naphthalimide 4-position,giving intensely coloured gels.These results describe previously unknown coordination chemistry and physical properties of the widely-used 1,8-naphthalimide backbone,and outline the important role played by subtle geometric variations in the physical characteristics of supramolecular metallogels.展开更多
基金the Irish Research Council(IRC)for a post-doctoral fellowship(GOIPD/2015/446 to CSH)Science Foundation Ireland(SFI)for SFI PI Awards(10/IN.1/B2999 and 13/IA/1865 to TG and TG13/IA/1926 to MM)+1 种基金SFI RFP G22226/RFP-1/MTR/3135(to MM),MPNS COST Actions MP1106 and MP1305,ESA(A0-99-075 and contract 4000115113)TCD Dean of Research Pathfinder Award(TG and CSH),the School of Chemistry,University of Southampton and the School of Chemistry,Trinity College Dublin for financial support.
文摘We have prepared a series of N-picolyl-1,8-naphthalimide derivatives and explored their coordination chemistry with d-block metal ions in the solid and solution states,and exploited the structural and chemical properties of these ligands to generate a family of robust metallogels.The 2-picolyl substituted ligands N-(2-picolyl)-1,8-naphthalimide L1 and N-(2-picolyl)-4-nitro-1,8-naphthalimide L2 showed interesting coordination behaviour in Mn,Co and Zn complexes 1-5,chelating through the pyridyl nitrogen atom and naphthalimide oxygen atom with subsequent bond localisation in the imide ring,the first example of such coordination behaviour to be structurally characterised.The 3-picolyl substituted ligands N-(3-picolyl)-1,8-naphthalimide L3 and N-(3-picolyl)-4-nitro-1,8-naphthalimide L4 vary in their coordination behaviour;the 4-unsubstituted ligand L3 acts as a simple monodentate donor giving crystalline assemblies,while the 4-nitro analogue L4 instead forms robust metallogels on reaction with Mn^(II) or Co^(II).The gels were found to be thermally and chemically reversible under various stimuli,and similar materials could be generated by installing a piperidinyl substituent at the naphthalimide 4-position,giving intensely coloured gels.These results describe previously unknown coordination chemistry and physical properties of the widely-used 1,8-naphthalimide backbone,and outline the important role played by subtle geometric variations in the physical characteristics of supramolecular metallogels.
