Photocatalytic Reduction of CO2 to CO in Aqueous Solution under Red-Light Irradiation by a Zn-Porphyrin-Sensitized Mn(I) Catalyst.

This work demonstrates photocatalytic CO2 reduction by a noble-metal-free photosensitizer-catalyst system in aqueous solution under red-light irradiation. A water-soluble Mn(I) tricarbonyl diimine complex, [MnBr(4,4'-{Et2O3PCH2}2-2,2'-bipyridyl)(CO)3] (1), has been fully characterized, including single-crystal X-ray crystallography, and shown to reduce CO2 to CO following photosensitization by tetra(N-methyl-4-pyridyl)porphyrin Zn(II) tetrachloride [Zn(TMPyP)]Cl4 (2) under 625 nm irradiation. This is the first example of 2 employed as a photosensitizer for CO2 reduction. The incorporation of -P(O)(OEt)2 groups, decoupled from the core of the catalyst by a -CH2- spacer, afforded water solubility without compromising the electronic properties of the catalyst. The photostability of the active Mn(I) catalyst over prolonged periods of irradiation with red light was confirmed by 1H and 13C{1H} NMR spectroscopy. This first report on Mn(I) species as a homogeneous photocatalyst, working in water and under red light, illustrates further future prospects of intrinsically photounstable Mn(I) complexes as solar-driven catalysts in an aqueous environment.

Manganese Tricarbonyl Complexes with Asymmetric 2-Iminopyridine Ligands: Toward Decoupling Steric and Electronic Factors in Electrocatalytic CO2 Reduction.

Manganese tricarbonyl bromide complexes incorporating IP (2-(phenylimino)pyridine) derivatives, [MnBr(CO)3(IP)], are demonstrated as a new group of catalysts for CO2 reduction, which represent the first example of utilization of (phenylimino)pyridine ligands on manganese centers for this purpose. The key feature is the asymmetric structure of the redox-noninnocent ligand that permits independent tuning of its steric and electronic properties. The α-diimine ligands and five new Mn(I) compounds have been synthesized, isolated in high yields, and fully characterized, including X-ray crystallography. Their electrochemical and electrocatalytic behavior was investigated using cyclic voltammetry and UV-vis-IR spectroelectrochemistry within an OTTLE cell. Mechanistic investigations under an inert atmosphere have revealed differences in the nature of the reduction products as a function of steric bulk of the ligand. The direct ECE (electrochemical-chemical-electrochemical) formation of a five-coordinate anion [Mn(CO)3(IP)]-, a product of two-electron reduction of the parent complex, is observed in the case of the bulky DIPIMP (2-[((2,6-diisopropylphenyl)imino)methyl]pyridine), TBIMP (2-[((2-tert-butylphenyl)imino)methyl]pyridine), and TBIEP (2-[((2-tert-butylphenyl)imino)ethyl]pyridine) derivatives. This process is replaced for the least sterically demanding IP ligand in [MnBr(CO)3(IMP)] (2-[(phenylimino)methyl]pyridine) by the stepwise formation of such a monoanion via an ECEC(E) mechanism involving also the intermediate Mn-Mn dimer [Mn(CO)3(IMP)]2. The complex [MnBr(CO)3(IPIMP)] (2-[((2-diisopropylphenyl)imino)methyl]pyridine), which carries a moderately electron donating, moderately bulky IP ligand, shows an intermediate behavior where both the five-coordinate anion and its dimeric precursor are jointly detected on the time scale of the spectroelectrochemical experiments. Under an atmosphere of CO2 the studied complexes, except for the DIPIMP derivative, rapidly coordinate CO2, forming stable bicarbonate intermediates, with no dimer being observed. Such behavior indicates that the CO2 binding is outcompeting another pathway: viz., the dimerization reaction between the five-coordinate anion and the neutral parent complex. The bicarbonate intermediate species undergo reduction at more negative potentials (ca. -2.2 V vs Fc/Fc+), recovering [Mn(CO)3(IP)]- and triggering the catalytic production of CO.

Sterically hindered Re- and Mn-CO2 reduction catalysts for solar energy conversion.

Novel molecular Re and Mn tricarbonyl complexes bearing a bipyridyl ligand functionalised with sterically hindering substituents in the 6,6'-position, [M(HPEAB)(CO)3(X)] (M/X = Re/Cl, Mn/Br; HPEAB = 6,6'-{N-(4-hexylphenyl)-N(ethyl)-amido}-2,2'-bipyridine) have been synthesised, fully characterised including by single crystal X-ray crystallography, and their propensity to act as catalysts for the electrochemical and photochemical reduction of CO2 has been established. Controlled potential electrolysis showed that the catalysts are effective for electrochemical CO2-reduction, yielding CO as the product (in MeCN for the Re-complex, in 95 : 5 (v/v) MeCN : H2O mixture for the Mn-complex). The recyclability of the catalysts was demonstrated through replenishment of CO2 within solution. The novel catalysts had similar reduction potentials to previously reported complexes of similar structure, and results of the foot-of-the-wave analysis showed comparable maximum turnover rates, too. The tentative mechanisms for activation of the pre-catalysts were proposed on the basis of IR-spectroelectrochemical data aided by DFT calculations. It is shown that the typical dimerisation of the Mn-catalyst was prevented by incorporation of sterically hindering groups, whilst the Re-catalyst undergoes the usual mechanism following chloride ion loss. No photochemical CO2 reduction was observed for the rhenium complex in the presence of a sacrificial donor (triethylamine), which was attributed to the short triplet excited state lifetime (3.6 ns), insufficient for diffusion-controlled electron transfer. Importantly, [Mn(HPEAB)(CO)3Br] can act as a CO2 reduction catalyst when photosensitised by a zinc porphyrin under red light irradiation (λ > 600 nm) in MeCN : H2O (95 : 5); there has been only one reported example of photoactivating Mn-catalysts with porphyrins in this manner. Thus, this work demonstrates the wide utility of sterically protected Re- and Mn-diimine carbonyl catalysts, where the rate and yield of CO-production can be adjusted based on the metal centre and catalytic conditions, with the advantage of suppressing unwanted side-reactions through steric protection of the vacant coordination site.

Sensitisation of Eu(III)- and Tb(III)-based luminescence by Ir(III) units in Ir/lanthanide dyads: evidence for parallel energy-transfer and electron-transfer based mechanisms.

A series of blue-luminescent Ir(III) complexes with a pendant binding site for lanthanide(III) ions has been synthesized and used to prepare Ir(III)/Ln(III) dyads (Ln = Eu, Tb, Gd). Photophysical studies were used to establish mechanisms of Ir→Ln (Ln = Tb, Eu) energy-transfer. In the Ir/Gd dyads, where direct Ir→Gd energy-transfer is not possible, significant quenching of Ir-based luminescence nonetheless occurred; this can be ascribed to photoinduced electron-transfer from the photo-excited Ir unit (*Ir, (3)MLCT/(3)LC excited state) to the pendant pyrazolyl-pyridine site which becomes a good electron-acceptor when coordinated to an electropositive Gd(III) centre. This electron transfer quenches the Ir-based luminescence, leading to formation of a charge-separated {Ir(4+)}˙-(pyrazolyl-pyridine)˙(-) state, which is short-lived possibly due to fast back electron-transfer (<20 ns). In the Ir/Tb and Ir/Eu dyads this electron-transfer pathway is again operative and leads to sensitisation of Eu-based and Tb-based emission using the energy liberated from the back electron-transfer process. In addition direct Dexter-type Ir→Ln (Ln = Tb, Eu) energy-transfer occurs on a similar timescale, meaning that there are two parallel mechanisms by which excitation energy can be transferred from *Ir to the Eu/Tb centre. Time-resolved luminescence measurements on the sensitised Eu-based emission showed both fast and slow rise-time components, associated with the PET-based and Dexter-based energy-transfer mechanisms respectively. In the Ir/Tb dyads, the Ir→Tb energy-transfer is only just thermodynamically favourable, leading to rapid Tb→Ir thermally-activated back energy-transfer and non-radiative deactivation to an extent that depends on the precise energy gap between the *Ir and Tb-based (5)D4 states. Thus, the sensitised Tb(iii)-based emission is weak and unusually short-lived due to back energy transfer, but nonetheless represents rare examples of Tb(III) sensitisation by a energy donor that could be excited using visible light as opposed to the usually required UV excitation.

Dynamics of ground and excited state vibrational relaxation and energy transfer in transition metal carbonyls.

Nonlinear vibrational spectroscopy provides insights into the dynamics of vibrational energy transfer in and between molecules, a crucial phenomenon in condensed phase physics, chemistry, and biology. Here we use frequency-domain 2-dimensional infrared (2DIR) spectroscopy to investigate the vibrational relaxation (VR) and vibrational energy transfer (VET) rates in different solvents in both the electronic ground and excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine), a prototypical transition metal carbonyl complex. The strong C≡O and ester C═O stretch infrared reporters, located on opposite sides of the molecule, were monitored in the 1600-2100 cm(-1) spectral region. VR in the lowest charge transfer triplet excited state ((3)CT) is found to be up to eight times faster than in the ground state. In the ground state, intramolecular anharmonic coupling may be solvent-assisted through solvent-induced frequency and charge fluctuations, and as such VR rates are solvent-dependent. In contrast, VR rates in the solvated (3)CT state are surprisingly solvent-insensitive, which suggests that predominantly intramolecular effects are responsible for the rapid vibrational deactivation. The increased VR rates in the excited state are discussed in terms of intramolecular electrostatic interactions helping overcome structural and thermodynamic barriers for this process in the vicinity of the central heavy atom, a feature which may be of significance to nonequilibrium photoinduced processes observed in transition metal complexes in general.

Contrasting simulated past and future responses of the Amazonian forest to atmospheric change.

Modelling simulations of palaeoclimate and past vegetation form and function can contribute to global change research by constraining predictions of potential earth system responses to future warming, and by providing useful insights into the ecophysiological tolerances and threshold responses of plants to varying degrees of atmospheric change. We contrasted HadCM3LC simulations of Amazonian forest at the last glacial maximum (LGM; 21 kyr ago) and a Younger Dryas-like period (13-12 kyr ago) with predicted responses of future warming to provide estimates of the climatic limits under which the Amazon forest remains relatively stable. Our simulations indicate that despite lower atmospheric CO2 concentrations and increased aridity during the LGM, Amazonia remains mostly forested, and that the cooling climate of the Younger Dryas-like period in fact causes a trend toward increased above-ground carbon balance relative to today. The vegetation feedbacks responsible for maintaining forest integrity in past climates (i.e. decreased evapotranspiration and reduced plant respiration) cannot be maintained into the future. Although elevated atmospheric CO2 contributes to a positive enhancement of plant carbon and water balance, decreased stomatal conductance and increased plant and soil respiration cause a positive feedback that amplifies localized drying and climate warming. We speculate that the Amazonian forest is currently near its critical resiliency threshold, and that even minor climate warming may be sufficient to promote deleterious feedbacks on forest integrity.