Structural variety of 5-fluoroarene-2-aminopyrimidine in comparison to 2-aminopyrimidine silver(i) coordination polymers: progress report and overview

Abstract

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)-2aminopyrimidine (OFAP) and 5-(p-dimethylaminotetrafluorophenyl)-2-aminopyrimidine (NFAP), and different counterions (OTf 2 , TFA 2 , ClO 4 2 , NO 3 2). 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 Ag-Ag distance (8, 3.049 Å), 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 Ag … Ag 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.

Driving Nonlinear Optical Activity with Dipolar 2-Aminopyrimidinium Cations in (C4H6N3)+(H2PO3)−

“…The LIDT is estimated to be 681 MW cm −2 at 1064 nm, which is approximately 1.7 times greater than that of KDP (406 MW cm −2 ) and comparable to that of 4HPP (882 MW cm −2 at 1064 nm). 7 As shown in Figure 5, the 2APP crystal also emits a purple fluorescence centered at 382 nm, which is ascribed to the π → π* and n → π* transitions, 23,24 which are similar to those of the related 2AP derivatives, such as 5-pentafluorophenyl-2aminopyrimidine (FAP) (λ em = 387 nm), 23 5-(p-methoxytetrafluorophenyl)-2-aminopyrimidine (OFAP) (λ em = 376 nm), 23 5-(p-dimethylaminotetrafluorophenyl)-2-aminopyrimidine (NFAP) (λ em = 395 nm), 23 and 2-amino-4-phenyl-6methylpyrimidine (L) (λ em = 375 nm). 24 More remarkably, the fluorescence quantum yield of the 2APP solid (Φ = 30.6%) is much higher than those of the 2AP solid and its derivatives, such as 2AP (Φ = 0.075%), 23,25 2-amino-4-phenyl-6m e t h y l p y r i m i d i n e ( L ) ( Φ = 9 .…”

Luminescent silver(i) coordination architectures containing 2-aminopyrimidyl ligands

“…Mattay's group used 5-polyfluoroarene-2-aminopyrimidine as a ligand to obtain a series of 1D AgIJI) coordination polymers with different counteranions (26-30 and 59-62). 40,50 Compound 26 showed double-strands bridged by an μ 2 -O:O′ ClO 4…”

“…Mattay's group showed that the polyfluoroarene-2-aminopyrimidine also could be used to obtain a series of 2D AgIJI) coordination layers modulated by anions (76-79). 40 In the chain of 76, the fluoroarene tail points to the same direction and forms weak π⋯π interaction (centroid distance: 3.70 Å) 62 with fluoroarene of the adjacent chain. In 77, the fluoroarene tail arranges toward the same direction, giving parallel alignment of the ligands.…”

An experimental and theoretical study of the kinetics and mechanism of hydroxyl radical reaction with 2-aminopyrimidine

“…19 The ability of 2Apy and its functionalized compounds to form molecular architectures via strong intermolecular hydrogen bonds and p-p interactions make them suitable for designing supramolecular architectures. [20][21][22][23][24] The present work is devoted to the study of the reactions of cOH with 2Apy in aqueous medium using pulse radiolysis with optical absorption detection. A trustworthy computational protocol by one author of this article and his co-worker 25 designed recently for getting the accurate kinetic data for radical-molecule reactions in solution have been applied for identifying appropriate mechanism (from RAF, SET, and HT) operated in the experiment.…”