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Metal-cyclen complexes have a number of important applications. However, the coordination chemistry between metal ions and cyclen-based macrocycles is much less well studied compared to their metal ion-crown ether analogues. This work, which makes a contribution to address this imbalance by studying complex ions of the type [M(Me 4 cyclen)(L)] + , was initiated by results of an experimental study which prepared some Group 1 metal cyclen complexes, namely [Li(Me 4 cyclen)(H 2 O)][BAr F ] and [Na(Me 4 cyclen)(THF)][BAr F ] and obtained their X-ray crystal structures [J. M. Dyke, W. Levason, M. E. Light, D. Pugh, G. Reid, H. Bhakhoa, P. Ramasami, and L. Rhyman, Dalton Trans., 2015, 44, 13853]. The lowest [M(Me 4 cyclen)(L)] + minimum energy structures (M = Li, Na, K, and L = H 2 O, THF, DEE, MeOH, DCM) are studied using density functional theory (DFT) calculations. The geometry of each [M(Me 4 cyclen)(L)] + structure and, in particular, the conformation of L are found to be mainly governed by steric hindrance which decreases as the size of the ionic radius increases from Li + → Na + → K + . Good agreement of computed geometrical parameters of [Li(Me 4 cyclen)(H 2 O)] + and [Na(Me 4 cyclen)(THF)] + with the corresponding geometrical parameters derived from the crystal structures [Li(Me 4 cyclen)(H 2 O)] + [BAr F ] - and [Na(Me 4 cyclen)(THF)] + [BAr F ] - is obtained. Bonding analysis indicates that the stability of the [M(Me 4 cyclen)(L)] + structures originates mainly from ionic interaction between the Me 4 cyclen/L ligands and the M + centres. The experimental observation that [M(Me 4 cyclen)(L)] + [BAr F ] - complexes could be prepared in crystalline form for M + = Li + and Na + , but that experiments aimed at synthesising the corresponding K + , Rb + , and Cs + complexes failed resulting in formation of [Me 4 cyclenH][BAr F ] is investigated using DFT and explicitly correlated calculations, and explained by considering production of [Me 4 cyclenH] + by a hydrolysis reaction, involving traces of water, which competes with [M(Me 4 cyclen)(L)] + formation. [Me 4 cyclenH] + formation dominates for M + = K + , Rb + , and Cs + whereas formation of [M(Me 4 cyclen)(L)] + is energetically favoured for M + = Li + and Na + . The results indicate that the number and type of ligands, play a key role in stabilising the [M(Me 4 cyclen)] + complexes and it is hoped that this work will encourage experimentalists to prepare and characterise other [M(Me 4 cyclen)(L)] + complexes.

A study of the Group 1 metal tetra-aza macrocyclic complexes [M(Me4cyclen)(L)]+ using electronic structure calculations

A study of the Group 1 metal tetra-aza macrocyclic complexes [M(Me₄cyclen)(L)]⁺ using electronic structure calculations