TY - JOUR
T1 - Synthesis and photobiological evaluation of Ru(II) complexes with expanded chelate polypyridyl ligands
AU - Ryan, Raphael T.
AU - Hachey, Austin C.
AU - Stevens, Kimberly
AU - Parkin, Sean R.
AU - Mitchell, Richard J.
AU - Selegue, John P.
AU - Heidary, David K.
AU - Glazer, Edith C.
N1 - Publisher Copyright:
© 2022
PY - 2023/1
Y1 - 2023/1
N2 - Photoreactive Ru(II) complexes capable of ejecting ligands have been used extensively for photocaging applications and for the creation of “photocisplatin” reagents. The incorporation of distortion into the structure of the coordination complex lowers the energy of dissociative excited states, increasing the yield of the photosubstitution reaction. While steric clash between ligands induced by adding substituents at the coordinating face of the ligand has been extensively utilized, a lesser known, more subtle approach is to distort the coordination sphere by altering the chelate ring size. Here a systematic study was performed to alter metal-ligand bond lengths, angles, and to cause intraligand distortion by introducing a “linker” atom or group between two pyridine rings. The synthesis, photochemistry, and photobiology of five Ru(II) complexes containing CH2, NH, O, and S-linked dipyridine ligands was investigated. All systems where stable in the dark, and three of the five were photochemically active in buffer. While a clear periodic trend was not observed, this study lays the foundation for the creation of photoactive systems utilizing an alternative type of distortion to facilitate photosubstitution reactions.
AB - Photoreactive Ru(II) complexes capable of ejecting ligands have been used extensively for photocaging applications and for the creation of “photocisplatin” reagents. The incorporation of distortion into the structure of the coordination complex lowers the energy of dissociative excited states, increasing the yield of the photosubstitution reaction. While steric clash between ligands induced by adding substituents at the coordinating face of the ligand has been extensively utilized, a lesser known, more subtle approach is to distort the coordination sphere by altering the chelate ring size. Here a systematic study was performed to alter metal-ligand bond lengths, angles, and to cause intraligand distortion by introducing a “linker” atom or group between two pyridine rings. The synthesis, photochemistry, and photobiology of five Ru(II) complexes containing CH2, NH, O, and S-linked dipyridine ligands was investigated. All systems where stable in the dark, and three of the five were photochemically active in buffer. While a clear periodic trend was not observed, this study lays the foundation for the creation of photoactive systems utilizing an alternative type of distortion to facilitate photosubstitution reactions.
KW - DNA
KW - Distortion
KW - Photocage
KW - Photochemistry
KW - Ruthenium
UR - http://www.scopus.com/inward/record.url?scp=85142939062&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85142939062&partnerID=8YFLogxK
U2 - 10.1016/j.jinorgbio.2022.112031
DO - 10.1016/j.jinorgbio.2022.112031
M3 - Article
C2 - 36327501
AN - SCOPUS:85142939062
SN - 0162-0134
VL - 238
JO - Journal of Inorganic Biochemistry
JF - Journal of Inorganic Biochemistry
M1 - 112031
ER -