Structural variety of 5-fluoroarene-2-aminopyrimidine in comparison to 2-aminopyrimidine silver(i) coordination polymers: progress report and overviewElectronic supplementary information (ESI) available: Details to materials and methods, synthesis of ligands 13 including NMR comparison, packing diagrams of the CPs 411, optical, fluorescence and powder diffraction data of the ligands, infrared spectroscopic data of all compounds, calculated atom coordinates of 13, and histograms of data from Tabl

A variety of fluoroarene-2-aminopyrimidine (FAP) silver( i ) coordination polymers (CPs) has been synthesized based on newly synthesized FAP derivatives, namely 5-( p -methoxytetrafluorophenyl)-2-aminopyrimidine (OFAP) and 5-( p -dimethylaminotetrafluorophenyl)-2-aminopyrimidine (NFAP), and different counterions (OTf , TFA , ClO 4 , NO 3 ). Their solid-state assembly as well as optical properties in terms of luminescence and infrared (IR) spectroscopy were investigated. Out of the several structures described herein, we obtained isomorphic CPs to previous studies ( 5 , 9 ), a CP architecture with a short AgAg distance ( 8 , 3.049 ), but also polymorphic crystals of [Ag(nfap)NO 3 ] n ( 11a , 11b ) and the latter showed differences in color and luminescence emission. Polymorphism gives an unparalleled possibility to investigate the origin of such phenomena since luminescence emission is quite often observed for these silver-hybrid solid-state materials and in several cases AgAg interactions are attributed for this phenomenon. We show that this explanation does not necessarily have to be the only one. Therefore we focus also on structural relationships and differences in a comprehensive comparison of our own and other known systems to start a more systematic description of the rich coordination capabilities of FAP and congeneric 2-aminopyrimidine (2-AP) based silver( i ) coordination polymers and networks. Density functional theory (DFT) calculations with periodic boundary conditions based on a plane wave basis are used to better understand the electronic structure of these crystalline materials. To complete the picture, steady-state spectroscopy studies (UV-Vis, fluorescence, IR) on all ligands and 2-AP itself were conducted as well as re-examination of the first reported CP of 2-AP and Ag I under the above aspects. Different coordination networks were obtained from various 5-fluoroarene-2-aminopyrimidines and silver salts, among them polymorphic crystals, which showed differences in color and luminescence.