Supramolecular Lone Pair−π/π−π/π−Anion Assembly in a Mg(II)−Malonate−2-Aminopyridine−Nitrate Ternary System

Abstract

The solid-state structure of an alkaline-earth metal complex reveals the formation of a remarkable supramolecular framework based on concurrent lone pair-pi, pi-pi, and pi-anion interactions whose stability has been investigated by density functional theory.

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

“…Examples of synthetic vectors for metal-based supramolecular synthesis include π· · · π [14][15][16], cation· · · π [17], anion· · · π [16,18,19], lone-pair· · · π [16,19,20], and metal· · · π [21,22] interactions, but the most common non-covalent interaction for such ventures is arguably the hydrogen bond [23][24][25][26][27]. Despite the relative frequent use of hydrogen bonds [28,29], such interactions are not always ideal since many hydrogen-bond donors (i.e., amines, oximes, and carboxylic acids) may forge unwanted coordinate-covalent bonds with the metal-ion leading to undesirable assemblies and architectures.…”

Experimental and theoretical study of uracil derivatives: the crucial role of weak fluorine–fluorine noncovalent interactions

“…33 Indeed, l.p.-p interactions have been found to be of great importance for the stabilization of biological macromolecules, as well as for the binding of inhibitors in the binding pocket of biochemical receptors. 34 More recently, in a comprehensive review, 35 Gamez et al defined such l.p.-p contacts as a new supramolecular bond and a rigorous analysis of the Cambridge Structure Database (CSD) revealed that such contacts are not unusual in organic/coordination compounds. This methodical analysis of the CSD clearly shows that l.p.-p interactions are actually ubiquitous in solid-state structures (such as the supramolecular anion-p contacts 36 ).…”

Co-operation of π⋯π, Cu(II)⋯π, carbonyl⋯π and hydrogen-bonding forces leading to the formation of water cluster mimics observed in the reassessed crystal structure of [Cu(mal)(phen)(H2O)]2·3H2O (H2mal=malonic acid, phen=1,10-phenanthroline)

“…The hydrogen bonded supramolecular dimer (Fig. 2) is additionally stabilized by the recently recognized novel carbonyl-p interaction [40][41][42][43][44][45][46][47][48]. Here it operates between the carboxylate C(30)@O(8) group of the malonato ligand bound to Cu(2) and the p system of the ring N1/C1/C5/C4/C3/C2 belonging to the phenanthroline ligand coordinated to Cu(1) (Fig.…”

“…The complicacies and sophistication of self-assembly process is due to the presence of various possible interactions which can lead to many ways of assembling the building blocks. Usually the strength of these possible interactions also come in a wide range including strong covalent force, intermediate coordinative force [4][5][6][7] and various weak forces such as hydrogen bonding [8][9][10][11][12][13][14], pÁÁÁp interaction [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30], C-HÁÁÁp interaction [31,32], metalÁÁÁp [33][34][35][36][37][38], anionÁÁÁp interaction [39] and lone pairÁÁÁp interaction [40][41][42][43][44][45][46][47][48]. The existence of phenomena like polymorphism [49][50]…”