A semiconducting
molecule containing a thiol anchor group, namely
2-(5-mercaptothien-2-yl)-8-(thien-2-yl)-5-hexylthieno[3,4-
c
]pyrrole-4,6-dione (abbreviated as D-A-D-SH), was designed,
synthesized, and used as a ligand in nonstoichiometric quaternary
nanocrystals of composition Ag
1.0
In
3.1
Zn
1.0
S
4.0
(S
6.1
) to give an inorganic/organic
hybrid. Detailed NMR studies indicate that D-A-D-SH ligands are present
in two coordination spheres in the organic part of the hybrid: (i)
inner in which the ligand molecules form direct bonds with the nanocrystal
surface and (ii) outer in which the ligand molecules do not form direct
bonds with the inorganic core. Exchange of the initial ligands (stearic
acid and 1-aminooctadecane) for D-A-D-SH induces a distinct change
of the photoluminescence. Efficient red luminescence of nanocrystals
capped with initial ligands (λ
max
= 720 nm, quantum
yield = 67%) is totally quenched and green luminescence characteristic
of the ligand appears (λ
max
= 508 nm, quantum yield
= 10%). This change of the photoluminescence mechanism can be clarified
by a combination of electrochemical and spectroscopic investigations.
It can be demonstrated by cyclic voltammetry that new states appear
in the hybrid as a consequence of D-A-D-SH binding to the nanocrystals
surface. These states are located below the nanocrystal LUMO and above
its HOMO, respectively. They are concurrent to deeper donor and acceptor
states governing the red luminescence. As a result, energy transfer
from the nanocrystal HOMO and LUMO levels to the ligand states takes
place, leading to effective quenching of the red luminescence and
appearance of the green one.