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-dihydropyrazino1, 2, 3, 4-lmn]-1, 10-phenanthrolinium, Phen-dzp = (C₁₅H₁₄N₂)²⁺, 6,7-dihydro-5H-1, 4]diazepino1, 2, 3, 4-lmn]1,10]phenanthroline-4, 8-diium], have been synthesized via the self-assembly reaction in solution. The compound 1 possesses a two-dimensional supramolecular network linked by bridging thiocyanate groups. Complex 2 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 1 and 2, and these “planar” cations are effective guests to manipulate the aggregate structure of thiocyanatocuprates.