11 research outputs found
Synthesis, Structural Characterization, and Host–Guest Studies of Aminoquinonato-Bridged Re(I) Supramolecular Rectangles
Aminoquinonato
bridged ReÂ(I)-based metallarectangles have been constructed via an
orthogonal bonding approach. Self-assembly of Re<sub>2</sub>(CO)<sub>10</sub> and aminoquinone ligands in the presence of ditopic linear
pyridyl ligands has resulted in the formation of metallarectangles
of the general formula [{(CO)<sub>3</sub>ReÂ(μ-η<sup>4</sup>-L)ÂReÂ(CO)<sub>3</sub>}<sub>2</sub>Â(μ-N-L′-N)<sub>2</sub>] (<b>1</b>–<b>4</b>), wherein <b>1</b>, L = 2,5-bisÂ(<i>n</i>-butylamino)-1,4-benzoquinonato (bbbq)
and N-L′-N = 4,4′-bipyridine (bpy); <b>2</b>,
L = 2,5-bisÂ(phenethylamino)-1,4-benzoquinonato (bpbq) and N-L′-N
= 4,4′-bipyridine; <b>3</b>, L = 2,5-bisÂ(<i>n</i>-butylamino)-1,4-benzoquinonato (bbbq) and N-L′-N = <i>trans</i>-1,2-bisÂ(4-pyridyl)Âethylene (bpe) and <b>4</b>, L = 2,5-bisÂ(phenethylamino)-1,4-benzoquinonato (bpbq) and N-L′-N
= <i>trans</i>-1,2-bisÂ(4-pyridyl)Âethylene (bpe). Metallarectangles <b>1</b>–<b>4</b> have been characterized by elemental
analysis, IR, NMR, and UV–vis absorption spectroscopic techniques.
The molecular structures of <b>1</b> and <b>4</b> were
determined by single-crystal X-ray diffraction methods. The molecular
recognition capability of <b>1</b> and <b>3</b> with pyrene
and triphenylene has been investigated using UV–vis absorption
and emission spectroscopic techniques. The formation of host–guest
complex has been further corroborated by the single-crystal X-ray
structural evidence of carceplex system (<b>3</b>⊃pyrene)·(DMF)
Synthesis and Spectroscopic and Structural Characterization of Oxamidato-Bridged Rhenium(I) Supramolecular Rectangles with Ester Functionalization
Oxamidato-bridged ReÂ(I)-based supramolecular
rectangles with an
ester functionality have been synthesized via an orthogonal bonding
approach under solvothermal conditions. Self-assembly of Re<sub>2</sub>(CO)<sub>10</sub> and oxamide ligands (H<sub>2</sub>L1 = <i>N</i>,<i>N</i>′-dibutyloxamide, H<sub>2</sub>L2 = <i>N</i>,<i>N</i>′-dioctyloxamide,
H<sub>2</sub>L3 = <i>N</i>,<i>N</i>′-didodecyloxamide,
and H<sub>2</sub>L4 = <i>N</i>,<i>N</i>′-dibenzyloxamide)
with the pyridyl ligand phenyl-1,4-bisÂ(isonicotinate) (pbin) has resulted
in the formation of metallarectangles of general formula [{(CO)<sub>3</sub>ReÂ(μ-η<sup>4</sup>-L)ÂReÂ(CO)<sub>3</sub>}<sub>2</sub>(μ-pbin)<sub>2</sub>] (<b>1</b>–<b>4</b>), wherein L = <i>N</i>,<i>N</i>′-dibutyloxamidato
(<b>1</b>), <i>N</i>,<i>N</i>′-dioctyloxamidato
(<b>2</b>), <i>N</i>,<i>N</i>′-didodecyloxamidato
(<b>3</b>), <i>N</i>,<i>N</i>′-dibenzyloxamidato
(<b>4</b>) and pbin = phenyl-1,4-bisÂ(isonicotinate). The metallarectangles
have been characterized using spectroscopic techniques, and single-crystal
X-ray structures have been obtained for <b>1</b> and <b>4</b>. The guest binding ability of <b>2</b> has been investigated
with a few aromatic amines and an amino ketone using electronic absorption
and fluorescence emission spectroscopy, and the results revealed a
strong binding interaction between host–guest species. The
luminescence properties of <b>2</b> and <b>3</b> have
been tuned using organic–aqueous solvent mixtures
Self-assembly of Thiolato-Bridged Manganese(I)-Based Metallarectangles: One-pot Synthesis and Structural Characterization
A new series of thiolato-bridged
manganeseÂ(I)-based supramolecular rectangles have been achieved by
three-precursor self-assembly of Mn<sub>2</sub>(CO)<sub>10</sub>,
diaryl disulfides (RSSR), and linear ditopic azine ligands (L) [L
= pyrazine (pz), 4,4′-bipyridine (bpy), and <i>trans</i>-1,2-bisÂ(4-pyridyl)Âethylene (bpe)] using a one-pot synthetic strategy.
Oxidative addition of RSSR (diphenyl disulfide and <i>p</i>-tolyl disulfide) to manganese decacarbonyl in the presence of rigid
bidentate ligands (L) afforded metallarectangles of the general formula
[{(CO)<sub>3</sub>MnÂ(μ-SR)<sub>2</sub>MnÂ(CO)<sub>3</sub>}<sub>2</sub>(μ-L)<sub>2</sub>] (<b>1</b>–<b>6</b>). Compounds <b>1</b>–<b>6</b> were characterized
using elemental analyses and NMR, IR, and UV–vis absorption
spectroscopic techniques. The molecular structures of metallarectangles <b>1</b>, <b>3</b>, and <b>5</b> were elucidated by single-crystal
X-ray diffraction methods. The guest binding ability of <b>3</b> and <b>5</b> has been investigated with two aromatic guests
using electronic absorption and fluorescence emission spectroscopy,
and the results revealed a strong binding interaction between host–guest
species
Self-Assembly of Manganese(I)-Based Molecular Squares: Synthesis and Spectroscopic and Structural Characterization
Syntheses of manganeseÂ(I)-based molecular squares have
been accomplished
in facile one-pot reaction conditions at room temperature. Self-assembly
of eight components has resulted in the formation of M<sub>4</sub>L<sub>4</sub>-type metallacyclophanes [MnÂ(CO)<sub>3</sub>BrÂ(μ-L)]<sub>4</sub> (<b>1</b>–<b>3</b>) using pentacarbonylbromomanganese
as metal precursor and rigid azine ligands such as pyrazine, 4,4′-bipyridine,
and <i>trans</i>-1,2-bisÂ(4-pyridyl)Âethylene, respectively,
as bridging ligands. The metallacyclophanes have been characterized
on the basis of IR, NMR, and UV–vis spectroscopic techniques
and single-crystal X-ray diffraction methods
Multicomponent Self-Assembly of Thiolato- and Selenato-Bridged Ester-Functionalized Rhenium(I)-Based Trigonal Metallaprisms: Synthesis and Structural Characterization
Multicomponent self-assembly of Re<sub>2</sub>(CO)<sub>10</sub>, diaryl dichalcogenide ligands (REER), and
phenyl-1,3,5-trisÂ(isonicotinate)
(ptin) under solvothermal conditions has resulted in the formation
of chalcogen-bridged trigonal metallaprisms of the general formula
[{(CO)<sub>3</sub>ReÂ(μ-ER)<sub>2</sub>ReÂ(CO)<sub>3</sub>}<sub>3</sub>(μ<sub>3</sub>-ptin)<sub>2</sub>] (<b>1</b>–<b>5</b>), wherein E = S, Se and R = phenyl, <i>p</i>-tolyl,
benzyl. Oxidative addition of diaryl disulfide/diaryl diselenide to
Re<sub>2</sub>(CO)<sub>10</sub> with the ester-functionalized tritopic
linker ptin has yielded trigonal metallaprisms <b>1</b>–<b>5</b> under facile reaction conditions. The metallaprisms <b>1</b>–<b>5</b> have been characterized using elemental
analysis and IR, UV–vis, and NMR spectroscopic techniques.
Single-crystal X-ray structures have been obtained for <b>3</b> and <b>4</b>. The structural features and chirality of metallaprisms <b>3</b> and <b>4</b> in the solid state have been highlighted
Amide-Functionalized Chalcogen-Bridged Flexible Tetranuclear Rhenacycles: Synthesis, Characterization, Solvent Effect on the Structure, and Guest Binding
The
synthesis of flexible rheniumÂ(I)-based amide-functionalized
chalcogen-bridged tetranuclear metallacycles of general formula [{(CO)<sub>3</sub>ReÂ(μ-ER)<sub>2</sub>ReÂ(CO)<sub>3</sub>}<sub>2</sub>(μ-L)<sub>2</sub>] (<b>1–8</b>) was achieved by treating rhenium
carbonyl with dialkyl/diaryl chalcogenide (RE–ER; E = S and
Se) in the presence of ditopic flexible or semiflexible pyridyl ligand
with amide functionality (L = <i>N</i>,<i>N</i>′-bisÂ(4-pyridylcarboxamide)-1,2-ethane (bpce) and <i>N</i>,<i>N</i>′-bisÂ(4-(4-pyridylcarboxamide)Âphenyl)Âmethane
(bpcpm)). Compounds <b>1–8</b> were formed by multicomponent
self-assembly under one-pot reaction conditions via oxidative addition
of dialkyl/diaryl chalcogenide to rhenium carbonyl with pyridyl ligands.
The resultant metallacyclophanes were characterized using elemental
analyses, infrared, ultraviolet–visible, and NMR spectroscopic
techniques. Metallacyclophanes <b>1–3</b> and <b>7</b> were structurally characterized by single-crystal X-ray diffraction
methods. The solvent-induced structural change of flexible tetranuclear
metallacyclophane <b>2</b> was demonstrated by crystallizing <b>2</b> in dichloroethane and dimethylformamide. Molecular recognition
capabilities of <b>2</b> and <b>7</b> were studied with
few aromatic compounds containing ethereal linkages
Amide-Functionalized Chalcogen-Bridged Flexible Tetranuclear Rhenacycles: Synthesis, Characterization, Solvent Effect on the Structure, and Guest Binding
The
synthesis of flexible rheniumÂ(I)-based amide-functionalized
chalcogen-bridged tetranuclear metallacycles of general formula [{(CO)<sub>3</sub>ReÂ(μ-ER)<sub>2</sub>ReÂ(CO)<sub>3</sub>}<sub>2</sub>(μ-L)<sub>2</sub>] (<b>1–8</b>) was achieved by treating rhenium
carbonyl with dialkyl/diaryl chalcogenide (RE–ER; E = S and
Se) in the presence of ditopic flexible or semiflexible pyridyl ligand
with amide functionality (L = <i>N</i>,<i>N</i>′-bisÂ(4-pyridylcarboxamide)-1,2-ethane (bpce) and <i>N</i>,<i>N</i>′-bisÂ(4-(4-pyridylcarboxamide)Âphenyl)Âmethane
(bpcpm)). Compounds <b>1–8</b> were formed by multicomponent
self-assembly under one-pot reaction conditions via oxidative addition
of dialkyl/diaryl chalcogenide to rhenium carbonyl with pyridyl ligands.
The resultant metallacyclophanes were characterized using elemental
analyses, infrared, ultraviolet–visible, and NMR spectroscopic
techniques. Metallacyclophanes <b>1–3</b> and <b>7</b> were structurally characterized by single-crystal X-ray diffraction
methods. The solvent-induced structural change of flexible tetranuclear
metallacyclophane <b>2</b> was demonstrated by crystallizing <b>2</b> in dichloroethane and dimethylformamide. Molecular recognition
capabilities of <b>2</b> and <b>7</b> were studied with
few aromatic compounds containing ethereal linkages
One-Pot Synthesis of Ruthenium Metallacycles via Oxidative Addition of Diaryldichalcogen and Halogen across a Ru–Ru Bond
Oxidative addition of diaryldichalcogen
ligands (REER) to ruthenium carbonyl (Ru<sub>3</sub>(CO)<sub>12</sub>) followed by the addition of halogen (X<sub>2</sub>) afforded chalcogen-bridged
RuÂ(II)-based metallacycles of general formula [XÂ(CO)<sub>3</sub>RuÂ(μ-ER)<sub>2</sub>RuÂ(CO)<sub>3</sub>X] (<b>1</b>–<b>10</b>), where E = S, Se, and Te; R = phenyl, tolyl, and benzyl; and X
= Br and I. Compounds <b>1</b>–<b>10</b> were characterized
using IR, UV–vis, and NMR spectroscopic techniques. Molecular
structures of the metallacycles have been elucidated by single-crystal
X-ray diffraction methods that confirm the dimeric nature of metallacycles,
wherein the two RuÂ(CO)<sub>3</sub>X moieties are held together by
the bridging aryl chalcogenide ligands
One-Pot Synthesis of Ruthenium Metallacycles via Oxidative Addition of Diaryldichalcogen and Halogen across a Ru–Ru Bond
Oxidative addition of diaryldichalcogen
ligands (REER) to ruthenium carbonyl (Ru<sub>3</sub>(CO)<sub>12</sub>) followed by the addition of halogen (X<sub>2</sub>) afforded chalcogen-bridged
RuÂ(II)-based metallacycles of general formula [XÂ(CO)<sub>3</sub>RuÂ(μ-ER)<sub>2</sub>RuÂ(CO)<sub>3</sub>X] (<b>1</b>–<b>10</b>), where E = S, Se, and Te; R = phenyl, tolyl, and benzyl; and X
= Br and I. Compounds <b>1</b>–<b>10</b> were characterized
using IR, UV–vis, and NMR spectroscopic techniques. Molecular
structures of the metallacycles have been elucidated by single-crystal
X-ray diffraction methods that confirm the dimeric nature of metallacycles,
wherein the two RuÂ(CO)<sub>3</sub>X moieties are held together by
the bridging aryl chalcogenide ligands
Self-Assembly of Selenium-Bridged Rhenium(I)-Based Metalla Rectangles: Synthesis, Characterization, and Molecular Recognition Studies
Self-assembly
of the selenium-bridged novel metallacyclophanes [{(CO)<sub>3</sub>ReÂ(μ-SeR)<sub>2</sub>ReÂ(CO)<sub>3</sub>}<sub>2</sub>(μ-L)<sub>2</sub>] (<b>1</b>–<b>3</b>) has been accomplished
by treating diaryl diselenide with low-valent transition-metal carbonyl
and rigid bidentate azine ligands under one-pot reaction conditions.
The oxidative addition of diphenyl/dibenzyl diselenides to Re<sub>2</sub>(CO)<sub>10</sub> with 4,4′-bipyridine, <i>trans</i>-1,2-bisÂ(4-pyridyl)Âethylene, and 1,4-bisÂ[2-(4-pyridyl)Âethenyl]Âbenzene
afforded tetranuclear metallacyclophanes. These compounds have been
characterized by elemental analysis and IR, NMR, and UV–vis
absorption spectroscopic techniques. The molecular structures of metallacylophanes <b>1a</b>,<b>b</b> and <b>2</b> were determined by single-crystal
X-ray diffraction methods, and the crystal structures showed that
two selenium-bridged dirhenium metallacycles were linked by two bipyridyl
spacers and attained a framework of molecular rectangles. In addition,
the molecular recognition capabilities of the molecular rectangles <b>1a</b>,<b>b</b> and <b>2</b> with aromatic compounds
such as pyrene and triphenylene have been investigated by studying
their binding properties, using UV–visible absorption and fluorescence
emission spectrophotometric methods. The nature of the binding interactions
were further supported by single-crystal X-ray diffraction methods,
and the crystal structures of <b>1</b><b>b</b>·(pyrene)
and <b>1</b><b>b</b>·(triphenylene) revealed that
CH···π interactions are mainly responsible for
the binding of <b>1b</b> with pyrene and triphenylene