Role of spacers and substituents in the self-assembly process: Syntheses and characterization of two novel thiocyanatocuprates polymers

Two novel cation-induced complexes, {(Phen-dq) [Cu2(SCN)4]}n (1) and {(Phen-dzp) [Cu2(SCN)4]}n (2) [Phen-dq = (C14H12N2)2+, 5,6-dihydropyrazino[1, 2, 3, 4-lmn]-1, 10-phenanthrolinium, Phen-dzp = (C15H14N2)2+, 6,7-dihydro-5H-[1, 4]diazepino[1, 2, 3, 4-lmn][1,10]phenanthroline-4, 8-diium], have been synthesized via the self-assembly reaction in solution. The compound possesses a two-dimensional supramolecular network linked by bridging thiocyanate groups. Complex is also a two-dimensional polymeric architecture with the organic cation Phen-dzp trapped in it. Each Cu(I) atom is coordinated by two N atoms and two S atoms from four NCS groups to form a Cu2(NCS)2 rectangular dimer unit. In these two compounds, thanks to the difference from organic cations, the simple modification from Phen-dq to Phen-dzp leads to distinct structures between and , and these “planar” cations are effective guests to manipulate the aggregate structure of thiocyanatocuprates.