Cyclometalated ruthenium(II) complexes having acridine moieties have been synthesized and characterized by spectroscopic methods. Protonation of the acridine nitrogen of the ruthenium(II) complexes not only causes dynamic equilibrium with remote N-heterocyclic carbene Ru═C complexes but also generates the NAD(+)/NADH redox function driven by a proton-coupled two-electron transfer accompanying a reversible C-H bond formation in the pyridinium ring.

The binuclear copper complex [Cu(DQPD)]2 (where DQPD = deprotonated N,N-di(quinolin-8-yl)pyridine-2,6-dicarboxamide (DQPDH2)) was synthesised and characterised by various spectroscopic as well as electrochemical techniques. The binuclear copper complex was converted into a mononuclear one by the addition of 2 equivalents of pTsOH into [Cu(DQPD)]2. The interconversion between the dimer and monomer complex was studied through UV-Vis spectroscopy and cyclic voltammetry. The mononuclear copper complex showed high catalytic activity towards electrochemical proton reduction using acetic acid as the external proton source in 95 : 5 (v/v) DMF/HO. It showed an i/i (where i is the catalytic current in the presence of acetic acid and i is the reduction peak current in absence of acid) value of 24 and a turnover rate (TOF) of 111.70 s at a scan rate of 100 mV s at 25 °C. The [Cu(DQPD)]2 complex evolved hydrogen under the irradiation of visible light in the presence of fluorescein (Fl) as a photosensitizer and triethylamine (TEA) as the sacrificial electron donor with an initial TOF of 0.03 s with respect to the catalyst.

The complex Ni(DQPD) (where DQPD = deprotonated N(2),N(6)-di(quinolin-8-yl)pyridine-2,6-dicarboxamide (DQPDH2)) behaves as a visible light driven active catalyst to reduce protons from water when employed with the photosensitizer fluorescein (Fl) and triethylamine (TEA) as the sacrificial electron donor. The photocatalytic system shows very high activity, attaining 2160 turnovers and an initial turnover rate of 0.032 s(-1) with respect to the catalyst. The proposed electrocatalytic mechanism is of the CECE type (C is a chemical step protonation and E is the electrochemical step reduction), where the Ni(DQPD) catalyst undergoes rapid protonation at the non-coordinating nitrogen atom of the quinoline before undergoing reduction. The location of the pendant base is a key factor such that the N-H resulting from the protonation of the non-coordinating nitrogen atom of the quinoline is properly located to interact with the Ni-H hydride leading to heterocoupling between protons and hydrides. Theoretical calculations for the catalytic system were carried out using the density functional level of theory (DFT) and are consistent with a mechanism for catalysis in a polypyridine nickel system. This is the first report of a polypyridine based nickel catalyst where the pendant base is responsible for the internal proton relay towards the metal center through the heterocoupling between protons and hydrides to generate hydrogen.

Photoisomeric transformations in ruthenium polypyridyl complexes have been rarely reported. Herein we report the geometrical transformation of cyclometalated trans-[Ru(tpy)(PAD)(OH(2))](+) ([1](+)) to the cis-[Ru(tpy)(PAD)(OH(2))](+) ([1a](+)) (tpy = 2,2';6',2"-terpyridine, PAD = 2-(pyrid-2'-yl)acridine) isomer upon irradiation of visible light (λ ≥420 nm). Due to a proton-induced tautomeric equilibrium between the Ru-C bond and Ru═C coordination, the π* energy levels of PADH are lower than those of tpy by 12.61 and 12.24 kcal mol(-1), respectively, in [1](+) and [1a](+). Isomers [1](+) and [1a](+) both act as catalytic oxygen-evolving complexes (OECs) chemically as well as electrochemically.

The homodinuclear CoII helicate complex [CoII(DQPD)]2 (1) was prepared by treating [Co­(H2O)6]­(ClO4)2 with the deprotonated form of the ligand N 2,N 6-bis­(quinolin-8-yl)­pyridine-2,6-dicarboxamide (DQPDH2). Complex 1 represents a discrete homodinuclear helicate complex with two CoII centers having a distorted-octahedral geometry through an unprecedented pyridine bridge. Complex 1, upon treatment with H2O2, undergoes oxidation at one of the CoII centers followed by a structural deformation to generate the mixed-valence complex [CoIIICoII(DQPD)2]­(ClO4) (2·ClO 4 ). In complex 2, the bridging through the central pyridine collapses along with the formation of Co­(III) octahedral and Co­(II) tetrahedral environments. Complexes 1 and 2 interconvert to one another. The effective magnetic moments for complexes 1 and 2 are respectively 5.88 and 4.30 μB. Complexes 1 and 2 have been employed for electrocatalytic proton reduction using AcOH as the proton source in 95/5 (v/v) DMF/H2O. A TOF of 30000 mmol of H2 h–1 (mol of 1)−1 at a potential of −1.7 V vs SCE was achieved. A resting-state analysis has been carried out to support the mechanism for the catalytic proton reduction.