Chromium Complex of Macrocyclic Ligands as Precursor for Nitric Oxide Release: A Theoretical Study

Our research on the chromium complex of macrocyclic ligands as a precursor for nitric oxide release makes a significant contribution to the field of chemistry. We conduct a detailed analysis of nitrito chromium complexes, specifically trans-[M(III)L^1-5(ONO)₂]⁺, where M=Cr(III) and L¹-L⁵ represent different ligands such as L¹=1,4,8,11-tetraazacyclotetradecane, L²= (5,7-dimethyl-6-benzylcyclam), L³= (5,7-dimethyl-6-anthracylcyclam), L⁴= (5,7-dimethyl-6-(p-hydroxymethylbenzyl)-1,4, 8,11-cyclam) and L⁵= (5,7-dimethyl-6-(1¢-methyl-4'-(1"-carboxymethylpyrene) benzyl)-1,4,8,11-tetraazacyclotetradecane). Our objective is to comprehensively understand the mechanism of NO release and identify the key factors influencing NO delivery. The optimized structure of the complexes at spin states S=1/2 or 3/2 indicates a decrease in the Cr(III)-O bond length (1.669-1.671 Å) along with an increase in the Cr(III)O-NO bond length (2.735-2.741 Å), which facilitates the release of NO. Furthermore, there is a significant change in the bond angle (Cr-O-NO), from 120.4° to 116.9°, to S=3/2, thus enlarging the O-NO bond and supporting the β-cleavage of NO from the complex. The calculated activation energy for the complexes reflects the energy difference between the low-spin doublet and high-spin quartet state due to spin crossover (SCO). Moreover, the Natural Transition Orbitals (NTOs) confirm the involvement of a hole-particle in the excitation. Additionally, TD-DFT reveals the pendant chromophore's role in generating NO, as the chromophore antenna effectively enhances light absorption.