TY - JOUR
T1 - Superphenylphosphines
T2 - Nanographene-Based Ligands That Control Coordination Geometry and Drive Supramolecular Assembly
AU - Smith, Jordan N.
AU - Hook, James M.
AU - Lucas, Nigel T.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/24
Y1 - 2018/1/24
N2 - Tertiary phosphines remain widely utilized in synthesis, most notably as supporting ligands in metal complexes. A series of triarylphosphines bearing one to three hexa-peri-hexabenzocoronene (HBC) substituents has been prepared by an efficient divergent route. These "superphenylphosphines", P{HBC(t-Bu) 5 } n Ph 3-n (n = 1-3), form the palladium complexes PdCl 2 L 2 and Pd 2 Cl 4 L 2 where the isomer distribution in solution is dependent on the number of HBC substituents. The crystalline structures of five complexes all show intramolecular π-stacking between HBC-phosphines to form a supramolecular bidentate-like ligand that distorts the metal coordination geometry. When n = 2 or 3, the additional HBC substituents engage in intermolecular π-stacking to assemble the complexes into continuous ribbons or sheets. The phosphines adopt HBC's characteristics including strong optical absorption, green emission, and redox activity.
AB - Tertiary phosphines remain widely utilized in synthesis, most notably as supporting ligands in metal complexes. A series of triarylphosphines bearing one to three hexa-peri-hexabenzocoronene (HBC) substituents has been prepared by an efficient divergent route. These "superphenylphosphines", P{HBC(t-Bu) 5 } n Ph 3-n (n = 1-3), form the palladium complexes PdCl 2 L 2 and Pd 2 Cl 4 L 2 where the isomer distribution in solution is dependent on the number of HBC substituents. The crystalline structures of five complexes all show intramolecular π-stacking between HBC-phosphines to form a supramolecular bidentate-like ligand that distorts the metal coordination geometry. When n = 2 or 3, the additional HBC substituents engage in intermolecular π-stacking to assemble the complexes into continuous ribbons or sheets. The phosphines adopt HBC's characteristics including strong optical absorption, green emission, and redox activity.
UR - http://www.scopus.com/inward/record.url?scp=85041200162&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b12251
DO - 10.1021/jacs.7b12251
M3 - Article
C2 - 29253338
AN - SCOPUS:85041200162
SN - 0002-7863
VL - 140
SP - 1131
EP - 1141
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -