Ruthenium Picolinate Complex as a Redox Photosensitizer With Wide-Band Absorption.

Ruthenium(II) picolinate complex, [Ru(dmb)2(pic)]+ (Ru(pic); dmb = 4,4'-dimethyl-2,2'-bipyridine; Hpic = picolinic acid) was newly synthesized as a potential redox photosensitizer with a wider wavelength range of visible-light absorption compared with [Ru(N∧N)3]2+ (N∧N = diimine ligand), which is the most widely used redox photosensitizer. Based on our investigation of its photophysical and electrochemical properties, Ru(pic) was found to display certain advantageous characteristics of wide-band absorption of visible light (λabs < 670 nm) and stronger reduction ability in a one-electron reduced state ( E 1 / 2 red = -1.86 V vs. Ag/AgNO3), which should function favorably in photon-absorption and electron transfer to the catalyst, respectively. Performing photocatalysis using Ru(pic) as a redox photosensitizer combined with a Re(I) catalyst reduced CO2 to CO under red-light irradiation (λex > 600 nm). TONCO reached 235 and ΦCO was 8.0%. Under these conditions, [Ru(dmb)3]2+ (Ru(dmb)) is not capable of working as a redox photosensitizer because it does not absorb light at λ > 560 nm. Even in irradiation conditions where both Ru(pic) and Ru(dmb) absorb light (λex > 500 nm), using Ru(pic) demonstrated faster CO formation (TOFCO = 6.7 min-1) and larger TONCO (2347) than Ru(dmb) (TOFCO = 3.6 min-1; TONCO = 2100). These results indicate that Ru(pic) is a superior redox photosensitizer over a wider wavelength range of visible-light absorption.

Photoelectrochemical CO2 reduction using a Ru(II)-Re(I) multinuclear metal complex on a p-type semiconducting NiO electrode.

A photocathode for CO2 reduction was successfully developed using a hybrid electrode comprising a Ru(II)-Re(I) supramolecular photocatalyst and a NiO electrode. Selective photoexcitation of the Ru photosensitizer unit of the photocatalyst at -1.2 V vs. Ag/AgNO3 selectively afforded CO with high faradaic efficiency.

A visible-light harvesting system for CO2 reduction using a Ru(II) -Re(I) photocatalyst adsorbed in mesoporous organosilica.

A photocatalytic system for CO2 reduction exhibiting visible-light harvesting was developed by preparing a hybrid consisting of a supramolecular metal complex as photocatalyst and periodic mesoporous organosilica (PMO) as light harvester. A Ru(II) Re(I) binuclear complex (RuRe) with methylphosphonic acid anchor groups was adsorbed on acridone or methylacridone embedded in the walls of PMO mesochannels to yield the hybrid structure. The embedded organic groups absorbed visible light, and the excitation energy was funneled to the Ru units. The energy accumulation was followed by electron transfer and catalytic reduction of CO2 to CO on the Re unit. The light harvesting of these hybrids enhanced the photocatalytic CO evolution rate by a factor of up to ten compared with that of RuRe adsorbed on mesoporous silica without a light harvester.

Hybridization between periodic mesoporous organosilica and a Ru(II) polypyridyl complex with phosphonic acid anchor groups.

A new method for the hybridization of a ruthenium(II) polypyridyl complex ([Ru(bpy)2((CH2PO3H2)2-bpy)](2+) (RuP2(2+): bpy =2,2'-bipyridine; (CH2PO3H2)2-bpy =2,2'-bipyridine-4,4'di(metylphosphonic acid)) with biphenylene-bearing periodic mesoporous organosilica (Bp-PMO made from 4,4'bis(triethoxysilyl)biphenyl [(C2H5O)3Si-(C6H4)2-Si(OC2H5)3]) was developed. Efficient and secure fixation of the ruthenium(II) complex with methylphosphonic acid groups (RuP2(2+)) in the mesopores of Bp-PMO occurred. This method introduced up to 660 µmol of RuP2(2+) in 1 g of Bp-PMO. Two modes of adsorption of RuP2(2+) in the mesopores of Bp-PMO were observed: one is caused by the chemical interaction between the methylphosphonic acid groups of RuP2(2+) and the silicate moieties of Bp-PMO and the other is attributed to aggregation of the RuP2(2+) complexes. In the case of the former mode, adsorbed RuP2(2+) (up to 80-100 µmol g(-1)) did not detach from Bp-PMO after washing with acetonitrile, dimethylformamide, or even water. Emission from the excited biphenylene (Bp) units was quantitatively quenched by the adsorbed RuP2(2+) molecules in cases where more than 60 µmol g(-1) of RuP2(2+) was adsorbed, and emission from RuP2(2+) was observed. Quantitative emission measurements indicated that emission from approximately 100 Bp units can be completely quenched by only one RuP2(2+) molecule in the mesopore, and photons absorbed by approximately 400 Bp units are potentially accumulated in one RuP2(2+) molecule.

Smallest optical gap for quasi-one-dimensional iodo-bridged platinum compounds.

We synthesized a series of one-dimensional (1D) iodo-bridged platinum compounds with long alkyl chains on the counterions. In the compounds, the shortest Pt···Pt distance and the smallest band gap thus far reported were achieved. These compounds were found to be in a CDW state by using synchrotron X-ray diffraction measurements.