Here, we describe
the neutral cyclometalated
tert-
butylisocyanide Pt
II
complexes, [Pt(C
∧
N)Cl(CNBu
t
)]
1
, the double
salts [Pt(C
∧
N)(CNBu
t
)
2
][Pt(C
∧
N)Cl
2
]
2
, and the cationic complexes [Pt(C
∧
N)(CNBu
t
)
2
]ClO
4
3
[C∧N = difluorophenylpyridine (dfppy,
a
), 4-(2-pyridyl)benzaldehyde
(ppy-CHO,
b
)]. A comparative study of the pseudopolymorphs
1a
,
1a·CHCl
3
,
1b
,
1b·0.5Toluene
,
1b·0.5PhF
, and
3a·0.25CH
2
Cl
2
reveals strong aggregation through Pt···Pt
and/or π···π stacking interactions to give
a variety of distinctive one-dimensional (1D) infinite chains, which
modulate the photoluminescent properties. This intermolecular long-range
aggregate formation is the main origin of the photoluminescent behavior
of
1a
and
1b
complexes, which exhibit highly
sensitive and reversible responses to multiple external stimuli including
different volatile organic compounds (VOCs), solvents, temperatures,
and pressures, with distinct color and phosphorescent color switching
from green to red. Furthermore, complex
1b
undergoes
supramolecular self-assembly
via
Pt···Pt
and/or π···π interactions into a polymer
thin polystyrene (PS) film 10 wt % in response to toluene vapors,
and
3a
exhibits vapochromic and vapoluminescent behavior.
Theoretical simulations on the dimer, trimer, and tetramer models
of
1a
and
1b
have been carried out to get
insight into the photophysical properties in the aggregated solid
state.
The production of Mesoporous Silica Nanoparticles (MSNs) with uniform textural characteristics and imaging properties in the large scale is still a challenge. Thus, the design of simple and scalable methods...
We present the synthesis and characterization of two
series of
mononuclear heteroleptic anionic cycloplatinated(II) complexes featuring
terminal cyanide ligand Q+[Pt(C^N)(p-MeC6H4)(CN)]− [C^N = benzoquinolate
(bzq), Q+ = K+
1 and NBu4
+
4; 2-phenylpyridinate (ppy), Q+ = K+
2 and NBu4
+
5 and 2-(2,4- difluorophenyl)pyridinate (dfppy), Q+ = K+
3 and NBu4
+
6] and a series of symmetrical binuclear complexes (NBu4)[Pt2(C^N)2(p-MeC6H4)2(μ-CN)] (C^N = bzq 7, ppy 8, dfppy 9). Compounds 5, 6, and 7–9 were further
determined by single-crystal X-ray diffraction. There are no apparent
intermolecular Pt···Pt interactions owing to the presence
of bulky NBu4
+ counterion. Slow crystallization
of K[Pt(ppy)(p-MeC6H4)(CN)] 2 in acetone/hexane evolves with formation of yellow crystals,
which were identified by single-crystal X-ray diffraction methods
as the salt complex {[Pt(ppy)(p-MeC6H4)(CN)]2K3(OCMe2)4(μ-OCMe2)2}[Pt(ppy)(p-MeC6H4)(μ-CN)Pt(ppy)(p-MeC6H4)]·2acetone (10),
featuring the binuclear anionic unit 8–
neutralized by an hybrid inorganic–organometallic coordination
polymer {[Pt(ppy)(p-MeC6H4)(CN)]2K3(OCMe2)4(μ-OCMe2)2}+. The photophysical properties of
all compounds were recorded in powder, polystyrene film, and solution
states with a quantum yield up to 21% for 9 in the solid
state. All complexes displayed bright emission in rigid media, and
for the interpretation of their absorption and emission properties,
density functional theory (DFT) and time-dependent DFT calculations
were applied.
Synthesis, photophysical, electrochemical properties and theoretical calculations of a series of dicationic tris-chelate PtIV complexes, which combine two cyclometalated 2-phenylbenzothiazole and phenanthroline-based ligands.
By using N,N-dibutyl-2,2’-bipyridine-4,4’-dicarboxamide as diimine (dbbpy) and distinctive cyclometalated groups, this work reports a new family of cationic phosphorescent Ir(III) cyclometaladed [Ir(C^N)2(N^N)]X compounds [C^N = difluorophenylpyridine (dfppy) a, 2,6-difluoro-3-(pyridin-2-yl)benzaldehyde (CHO-dfppy)...
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