Change in the Site of Electron‐Transfer Reduction of a Zinc–Quinoxalinoporphyrin/Gold–Quinoxalinoporphyrin Dyad by Binding of Scandium Ions and the Resulting Remarkable Elongation of the Charge‐Shifted‐State Lifetime

The site of electron‐transfer reduction of AuPQ+ (PQ=5,10,15,20‐tetrakis(3,5‐di‐tert‐butylphenyl)quino‐xalino[2, 3−b′]porphyrin) and AuQPQ+ (QPQ=5,10,15,20‐tetrakis(3,5‐di‐tert‐butylphenyl)bisquinoxalino[2,3‐b′:12,13‐b′′]porphyrin) is changed from the AuIII center to the quinoxaline part of the PQ macrocycle in the presence of Sc3+ in benzonitrile because of strong binding of Sc3+ to the two nitrogen atoms of the quinoxaline moiety. Strong binding of Sc3+ to the corresponding nitrogen atoms on the quinoxaline unit of ZnPQ also occurs for the neutral form. The effects of Sc3+ on the photodynamics of an electron donor–acceptor compound containing a linked ZnII and AuIII porphyrin ([ZnPQ–AuPQ]PF6) have been examined by femto‐ and nanosecond laser flash photolysis measurements. The observed transient absorption bands at 630 and 670 nm after laser pulse irradiation in the absence of Sc3+ in benzonitrile are assigned to the charge‐shifted (CS) state (ZnPQ.+–AuPQ). The CS state decays through back electron transfer (BET) to the ground state rather than to the triplet excited state. The BET rate was determined from the disappearance of the absorption band due to the CS state. The decay of the CS state obeys first‐order kinetics. The CS lifetime was determined to be 250 ps in benzonitrile. Addition of Sc3+ to a solution of ZnPQ–AuPQ+ in benzonitrile caused a drastic lengthening of the CS lifetime that was determined to be 430 ns, a value 1700 times longer than the 250 ps lifetime measured in the absence of Sc3+. Such remarkable prolongation of the CS lifetime in the presence of Sc3+ results from a change in the site of electron transfer from the AuIII center to the quinoxaline part of the PQ macrocycle when Sc3+ binds to the quinoxaline moiety, which decelerate BET due to a large reorganization energy of electron transfer. The change in the site of electron transfer was confirmed by ESR measurements, redox potentials, and UV/Vis spectra of the singly reduced products. Long lifetime! A dramatic effect of Sc3+ was observed on the electron‐transfer reduction of gold(III) quinoxalino‐ and bisquinoxalinoporphyrins (AuPQ+ and AuQPQ+) (see figure), which not only changes the site of electron transfer from the AuIII metal to the fused quinoxaline part of the PQ macrocycle, but also leads to a remarkable elongation of the lifetime of the charge‐shifted state of a ZnPQ–AuPQ dyad in benzonitrile. This is due to the strong binding of Sc3+ to the ZnPQ and AuPQ+ moieties.