RAFT copolymerization of Pt(II) pincer complexes with water-soluble
polymer as an efficient way to obtain micellar-type nanoparticles with
aggregation induced NIR emission.
Abstract
The idea of preparation a water-soluble Pt-containing AIEgen
successfully realized by direct RAFT copolymerization of a Pt(II)
complex ( LPtPV) containing a vinyl group and
polyvinylpyrrolidone ( p(VP)). The resulting block-copolymer
p(VP-b-LPtPV) containing 5-8 Pt(II) chromophores
exhibits intriguing photophysical properties - strong solvent and
concentration dependence of absorption and emission characteristics.
Various physicochemical and analytical methods (NMR spectroscopy, XRD
analysis, ESI-MS, AUC, DLS, ICP-OES, GPC, viscometry, TEM) were used to
characterize the initial complex, its binuclear analogues,
p(VP) and p(VP-b-LPtPV). The obtained data
indicate that the photophysical properties of the latter are dictated by
the type of aggregation process rather than solvatochromic effects. It
is shown that at low concentration in organic solvents the platinum
chromophores aggregation is either absent (DMF) or occurs predominantly
at intramolecular level (MeCN), whereas in aqueous media
p(VP-b-LPtPV) readily aggregates into micellar-type
nanoparticles with a hydrophilic p(VP) corona and a hydrophobic
Pt-containing core, in which strong intra- and intermolecular Pt···Pt
and/or π···π interactions result in a significant redshift of absorption
and emission down to 600 nm and 816 nm, respectively. Despite of
emission shift into NIR area where it is commonly quenched by
nonradiative vibrational relaxation increase in emission quantum yield
occurs in complete agreement with typical features of AIE emitters.
Quantum mechanics/molecular mechanics simulations of aggregation
processes also confirm the trends in the relationship between
aggregation mode and photophysical behavior, particularly, in the
variations of energy gaps between the ground state of the AIEgens and
their excited singlet and triplet states.