26 research outputs found
Konsep Proses Pemesinan Berkelanjutan
Metal industrial machining usually strongth pressure from all sectors, ether raw material industries or user metal industries. Manufacturint process which offered to all sectors industries or companies that sustainable manufakturing consist of three main factor are efective cost, enviroment and social performance
Fusing High Symmetric Coordination Polyhedrons of Cu<sub>6</sub>(PIP)<sub>4</sub>, Cu<sub>12</sub>(PIP)<sub>8</sub>, and Cu<sub>12</sub>(PIP)<sub>24</sub> into an Unprecedented Porous MOF: Synthesis, Structure, and Its Remarkable CO<sub>2</sub> Selectivity
An unprecedented metal–organic framework, NJU-Bai6,
formed by piling up the nanocages Cu<sub>6</sub>(PIP)<sub>4</sub>,
Cu<sub>12</sub>(PIP)<sub>8</sub>, and Cu<sub>12</sub>(PIP)<sub>24</sub> through sharing faces of the “opened” triangular
and square windows, has been designed and structurally characterized.
Very interestingly, it exhibits the third highest selectivity of CO<sub>2</sub> over N<sub>2</sub> with the value about 60 at room temperature
Fusing High Symmetric Coordination Polyhedrons of Cu<sub>6</sub>(PIP)<sub>4</sub>, Cu<sub>12</sub>(PIP)<sub>8</sub>, and Cu<sub>12</sub>(PIP)<sub>24</sub> into an Unprecedented Porous MOF: Synthesis, Structure, and Its Remarkable CO<sub>2</sub> Selectivity
An unprecedented metal–organic framework, NJU-Bai6,
formed by piling up the nanocages Cu<sub>6</sub>(PIP)<sub>4</sub>,
Cu<sub>12</sub>(PIP)<sub>8</sub>, and Cu<sub>12</sub>(PIP)<sub>24</sub> through sharing faces of the “opened” triangular
and square windows, has been designed and structurally characterized.
Very interestingly, it exhibits the third highest selectivity of CO<sub>2</sub> over N<sub>2</sub> with the value about 60 at room temperature
Isolation and X‑ray Crystal Structures of Triarylphosphine Radical Cations
Salts
containing triarylphosphine radical cations <b>1</b><sup><b>•+</b></sup> and <b>2</b><sup><b>•+</b></sup> have been isolated and characterized by electron paramagnetic
resonance (EPR) and UV–vis absorption spectroscopy as well
as single-crystal X-ray diffraction. Radical <b>1</b><sup><b>•+</b></sup> exhibits a relaxed pyramidal geometry, while
radical <b>2</b><sup><b>•+</b></sup> becomes fully
planar. EPR studies and theoretical calculations showed that the introduction
of bulky aryl groups leads to enhanced p character of the singly occupied
molecular orbital, and the radicals become less pyramidalized or fully
flattened
Isolation and X‑ray Crystal Structures of Triarylphosphine Radical Cations
Salts
containing triarylphosphine radical cations <b>1</b><sup><b>•+</b></sup> and <b>2</b><sup><b>•+</b></sup> have been isolated and characterized by electron paramagnetic
resonance (EPR) and UV–vis absorption spectroscopy as well
as single-crystal X-ray diffraction. Radical <b>1</b><sup><b>•+</b></sup> exhibits a relaxed pyramidal geometry, while
radical <b>2</b><sup><b>•+</b></sup> becomes fully
planar. EPR studies and theoretical calculations showed that the introduction
of bulky aryl groups leads to enhanced p character of the singly occupied
molecular orbital, and the radicals become less pyramidalized or fully
flattened
Isolation and X‑ray Crystal Structures of Triarylphosphine Radical Cations
Salts
containing triarylphosphine radical cations <b>1</b><sup><b>•+</b></sup> and <b>2</b><sup><b>•+</b></sup> have been isolated and characterized by electron paramagnetic
resonance (EPR) and UV–vis absorption spectroscopy as well
as single-crystal X-ray diffraction. Radical <b>1</b><sup><b>•+</b></sup> exhibits a relaxed pyramidal geometry, while
radical <b>2</b><sup><b>•+</b></sup> becomes fully
planar. EPR studies and theoretical calculations showed that the introduction
of bulky aryl groups leads to enhanced p character of the singly occupied
molecular orbital, and the radicals become less pyramidalized or fully
flattened
Unprecedented Boron-Functionalized Carborane Derivatives by Facile and Selective Cobalt-Induced B–H Activation
The
16-electron complex CpCoS<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub> (<b>1</b>) is found to react with the alkynes
HCî—ĽCCÂ(O)ÂR [R = methyl (Me), phenyl (Ph), styryl (St), ferrocenyl
(Fc)] at ambient temperature to give two types of 17-electron cobalt
complexes <b>2a</b>–<b>d</b> and <b>3a</b>–<b>d</b> containing unique B(3)/B(6)-norbornyl carborane
moieties. A formation mechanism via a tandem sequence of metal-induced
B–H activation, B–Cp formation, Cp delivery and Diels–Alder
addition is proposed on the basis of DFT calculations. The reactivity
of these paramagnetic 17-electron complexes has been studied: Exposed
to a combination of air, moisture and silica, complexes <b>2a</b>–<b>d</b> undergo alkyl C–S cleavage to give
16-electron complexes <b>4a</b>–<b>c</b> containing
a boron-norbornadienyl moiety, and simultaneous carboranyl C–S
cleavage to afford cobalt-free carborane derivatives <b>5a</b>–<b>d</b> containing a boron-norbornyl unit. Both <b>2a</b>–<b>d</b> and <b>3a</b>–<b>d</b> allow further alkyne insertion into the Co–S bond
to generate cobalt-free boron–norbornyl carborane derivatives
(<i>Z</i>/<i>E</i>)-<b>7a</b>–<b>d</b> and (<i>Z</i>/<i>E</i>)-<b>8a</b>–<b>d</b>, both containing a vinyl sulfido group. Addition
of AlCl<sub>3</sub> not only promotes the conversion of <b>2a</b>–<b>d</b>, but also leads predominantly to (<i>E</i>)-<b>9a</b>–<b>d</b> as retro-Diels–Alder
products. Upon heating, the isomerization from <i>E</i> to <i>Z-</i>configuration of the vinyl group and reorganization of
the norbornyl moiety of (<i>Z</i>/<i>E</i>)-<b>7a</b>–<b>d</b> occur to lead to (<i>Z</i>)-<b>9a</b>–<b>d</b> as well as the unexpected
[1,2]-H shifted products (<i>Z</i>)-<b>10b</b>,<b>c</b>. Thus, the 17-electron complexes <b>2a</b>–<b>d</b> and <b>3a</b>–<b>d</b> serve as intermediates
for synthesis of variety of boron-functionalized carborane derivatives.
In this study, efficient routes have been developed through cobalt-mediated
B–H activation to prepare boron-functionalized carborane derivatives
that are unavailable by conventional routes
Syntheses, Structures, Photochemical and Magnetic Properties of Novel Divalent Cd/Mn Coordination Polymers Based on a Semirigid Tripodal Carboxylate Ligand
The
reactions of a semirigid tripodal carboxylic ligand, 3,5-biÂ(4-carboxy-phenoxy)-benzoic
acid (H<sub>3</sub>BCPBA) with CdÂ(NO<sub>3</sub>)<sub>2</sub>/MnÂ(NO<sub>3</sub>)<sub>2</sub> afford five novel complexes, {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>·(DMA)<sub>2</sub>·(H<sub>2</sub>O)<sub>5</sub>]·7H<sub>2</sub>O·2DMA}<sub><i>n</i></sub> (<b>1</b>), {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>(L<sup>1</sup>)Â(H<sub>2</sub>O)<sub>6</sub>]·(L<sup>1</sup>)}<sub><i>n</i></sub> (L<sup>1</sup> = 4-[(E)-4-pyridinylazo]Âpyridine)
(<b>2</b>), {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>(L<sup>2</sup>)·(H<sub>2</sub>O)<sub>3</sub>(DMF)<sub>2</sub>]·2DMF}<sub><i>n</i></sub> (L<sup>2</sup> = 1,3-bisÂ(4-pyridyl)Âpropane)
(<b>3</b>), {[Mn<sub>3</sub>(BCPBA)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·11H<sub>2</sub>O}<sub><i>n</i></sub> (<b>4</b>), {[Mn<sub>3</sub>(BCPBA)<sub>2</sub>(DMF)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·2DMF·9H<sub>2</sub>O}<sub><i>n</i></sub> (<b>5</b>) in the presence
or absence of an auxiliary ligand. Compound <b>1</b> is a three-dimensional
(3D) structure with 3,4-connected net structure. Compound <b>2</b> possesses 3D networks with two 3D → 3D interpenetration frameworks.
Compound <b>3</b> is a 3D sheet structure with a decorated tfz-d
topology. Compound <b>4</b> is a 3D structure which consists
of a two-dimensional (2D) Mn honeycomb net with six infinite Mn rings
and BCPBA<sup>3–</sup> ligands. Compound <b>5</b> is
also a 3D structure, while its 2D Mn honeycomb net with eight infinite
Mn rings is different from that of compound <b>4</b>. The photochemical
property of <b>1</b>–<b>3</b> is performed in the
solid state at room temperature. Magnetic susceptibility measurements
indicate that compounds <b>4</b> and <b>5</b> exhibit
antiferromagnetic coupling between adjacent MnÂ(II) ions
Syntheses, Structures, Photochemical and Magnetic Properties of Novel Divalent Cd/Mn Coordination Polymers Based on a Semirigid Tripodal Carboxylate Ligand
The
reactions of a semirigid tripodal carboxylic ligand, 3,5-biÂ(4-carboxy-phenoxy)-benzoic
acid (H<sub>3</sub>BCPBA) with CdÂ(NO<sub>3</sub>)<sub>2</sub>/MnÂ(NO<sub>3</sub>)<sub>2</sub> afford five novel complexes, {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>·(DMA)<sub>2</sub>·(H<sub>2</sub>O)<sub>5</sub>]·7H<sub>2</sub>O·2DMA}<sub><i>n</i></sub> (<b>1</b>), {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>(L<sup>1</sup>)Â(H<sub>2</sub>O)<sub>6</sub>]·(L<sup>1</sup>)}<sub><i>n</i></sub> (L<sup>1</sup> = 4-[(E)-4-pyridinylazo]Âpyridine)
(<b>2</b>), {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>(L<sup>2</sup>)·(H<sub>2</sub>O)<sub>3</sub>(DMF)<sub>2</sub>]·2DMF}<sub><i>n</i></sub> (L<sup>2</sup> = 1,3-bisÂ(4-pyridyl)Âpropane)
(<b>3</b>), {[Mn<sub>3</sub>(BCPBA)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·11H<sub>2</sub>O}<sub><i>n</i></sub> (<b>4</b>), {[Mn<sub>3</sub>(BCPBA)<sub>2</sub>(DMF)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·2DMF·9H<sub>2</sub>O}<sub><i>n</i></sub> (<b>5</b>) in the presence
or absence of an auxiliary ligand. Compound <b>1</b> is a three-dimensional
(3D) structure with 3,4-connected net structure. Compound <b>2</b> possesses 3D networks with two 3D → 3D interpenetration frameworks.
Compound <b>3</b> is a 3D sheet structure with a decorated tfz-d
topology. Compound <b>4</b> is a 3D structure which consists
of a two-dimensional (2D) Mn honeycomb net with six infinite Mn rings
and BCPBA<sup>3–</sup> ligands. Compound <b>5</b> is
also a 3D structure, while its 2D Mn honeycomb net with eight infinite
Mn rings is different from that of compound <b>4</b>. The photochemical
property of <b>1</b>–<b>3</b> is performed in the
solid state at room temperature. Magnetic susceptibility measurements
indicate that compounds <b>4</b> and <b>5</b> exhibit
antiferromagnetic coupling between adjacent MnÂ(II) ions
Three 2D/2D → 2D or 3D Coordination Polymers: Parallel Stacked, Interpenetration, and Polycatenated
Three
fascinating coordination polymers, {[Zn<sub>2</sub>(TPPBDA)Â(HCO<sub>2</sub><sup>–</sup>)<sub>4</sub>]·2H<sub>2</sub>O}<sub><i>n</i></sub> (<b>1</b>), {[ZnÂ(TPPBDA)<sub>1/2</sub>(4,4′-sdb)]·2H<sub>2</sub>O }<sub><i>n</i></sub> (<b>2</b>), and {[ZnÂ(TPPBDA)<sub>1/2</sub>(oba)·2DMF·2H<sub>2</sub>O]}<sub><i>n</i></sub> (<b>3</b>), have been
successfully synthesized and characterized by the self-assembly of
the TPPDBA ligand as well as Zn<sup>2+</sup> metal salts, or in the
presence of carboxylate ligands (TPPDBA = <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetrakisÂ(4-(4-pyridine)-phenyl)
biphenyl-4,4′-diamine), 4,4′-H<sub>2</sub>sdb = 4,4′-sulfonyldibenzoate,
4,4′-H<sub>2</sub>oba = 4,4′-oxybisÂ(benzoate), DMF = <i>N</i>,<i>N</i>-dimethylformamide). In complex <b>1</b>, the 2D ABAB parallel stacked network in which left- and
right-handed helical chains coexist and array alternately (2D<sub>chiral</sub>/2D<sub>chiral</sub> → 2D<sub>achiral</sub>) makes <b>1</b> give rise to a new interesting 2D interwoven network. Complex <b>2</b> exhibits a 2D + 2D → 2D parallel interpenetrated
network. For compound <b>3</b>, the polycatenation among the
2D layer further extends the 2D net into a 3D framework