22 research outputs found
Peraturan Bersama Menteri Agama dan Menteri dalam Negeri Nomor 08 dan 09 Tahun 2006 Tentang Pendirian Rumah Ibadat (Kajian dalam Perspektif Hak Asasi Manusia )
Pundamental 1945 Constitution as the rule has been set explicitly for religious freedom in the run by followers, who belong to one human rights has, but in reality the persecution of religious life and often inevitable. Between religious persecution can come from various directions such as harassing each other, mutual intimidate(violence) and that most often occurs between religious persecution that is prihal establishment synagogue. Therefore, in terms of the establishment of the synagogue there must be government intervention to regulate it, if in this case given the freedom and without any clear rules, the sectarian conflict will not be able to avoid. One step from the government to avoid conflict in the establishment of the synagogue is to be issued the Joint Decree of the Minister of Religious Affairs and the Minister of Home Affairs Number 08 and Number 09 Year 2006 About the Construction of Houses of Worship that aims to create harmony and peace between religious and have certainty Strong law
Effect of the Cooling Rate on Dimerization of C<sub>60</sub><sup>•–</sup> in Fullerene Salt (DMI<sup>+</sup>)<sub>2</sub>·(C<sub>60</sub><sup>•–</sup>)·{Cd(Et<sub>2</sub>NCS<sub>2</sub>)<sub>2</sub>I<sup>–</sup>}
The salt (DMI<sup>+</sup>)<sub>2</sub>·(C<sub>60</sub><sup>•–</sup>)·{Cd(Et<sub>2</sub>NCS<sub>2</sub>)<sub>2</sub>I<sup>–</sup>} (<b>1</b>) containing fullerene
radical anions, the anions of cadmium diethyldithiocarbamate iodide,
and <i>N</i>,<i>N</i>′-dimethylimidazolium
cations was obtained. Fullerenes are monomeric in <b>1</b> at
250 K and form three-dimensional packing in which each fullerene has
nearly tetrahedral surroundings from neighboring fullerenes. Fullerenes
with a shorter interfullerene center-to-center distance of 10.031(2)
Å form spiral chains arranged along the lattice <i>c</i> axis. The convolution consists of four fullerene molecules. Dimerization
realized in <b>1</b> within the spiral chains below 135 K manifests
a strong dependence on the cooling rate. The “frozen”
monomeric phase was obtained upon instant quenching of <b>1</b>. This phase is stable below 95 K for a long time but slowly converted
to the dimeric phase at <i>T</i> > 95 K. It exhibits
a weak
antiferromagnetic interaction of spins below 95 K (the Weiss temperature
is −4 K), which results in the splitting of the electron paramagnetic
resonance (EPR) signal into two components below 10 K. A disordered
phase containing both C<sub>60</sub><sup>•–</sup> monomers
and singly bonded (C<sub>60</sub><sup>–</sup>)<sub>2</sub> dimers
with approximately 0.5/0.5 occupancies is formed at an intermediate
cooling rate (for 20 min). The position of each fullerene in this
phase is split into three positions slightly shifted relative to each
other. The central position corresponds to nonbonded fullerenes with
interfullerene center-to-center distances of 9.94–10.00 Å.
Two other positions are coincided to dimeric fullerenes formed with
the right and left fullerene neighbors within the spiral chain. This
intermediate phase is paramagnetic with nearly zero Weiss temperature
due to isolation of C<sub>60</sub><sup>•–</sup> by diamagnetic
species and exhibits a strongly asymmetric EPR signal below 20 K.
A diamagnetic phase containing ordered singly bonded (C<sub>60</sub><sup>–</sup>)<sub>2</sub> dimers can be obtained only upon
slow cooling of the crystal for 6 h
Linear Coordination Fullerene C<sub>60</sub> Polymer [{Ni(Me<sub>3</sub>P)<sub>2</sub>}(μ‑η<sup>2</sup>,η<sup>2</sup>‑C<sub>60</sub>)]<sub>∞</sub> Bridged by Zerovalent Nickel Atoms
Coordination nickel-bridged fullerene
polymer [{Ni(Me<sub>3</sub>P)<sub>2</sub>}(μ-η<sup>2</sup>,η<sup>2</sup>-C<sub>60</sub>)]<sub>∞</sub> (<b>1</b>) has been obtained via reduction of a Ni<sup>II</sup>(Me<sub>3</sub>P)<sub>2</sub>Cl<sub>2</sub> and C<sub>60</sub> mixture. Each nickel
atom is linked in the polymer with two fullerene units by η<sup>2</sup>-type Ni–C(C<sub>60</sub>) bonds of 2.087(8)–2.149(8)
Å length. Nickel atoms are coordinated to the 6–6 bonds
of C<sub>60</sub> as well as two trimethylphosphine ligands to form
a four-coordinated environment around the metal centers. Fullerene
cages approach very close to each other in the polymer with a 9.693(3)
Å interfullerene center-to-center distance, and two short interfullerene
C–C contacts of 2.923(7) Å length are formed. Polymer
chains are densely packed in a crystal with interfullerene center-to-center
distances between fullerenes from neighboring polymer chains of 9.933(3)
Å and multiple interfullerene C···C contacts.
As a result, three-dimensional dense fullerene packing is formed in <b>1</b>. According to optical and electron paramagnetic resonance
spectra, fullerenes are neutral in <b>1</b> and nickel atoms
have a zerovalent state with a diamagnetic d<sup>10</sup> electron
configuration. The density functional theory calculations prove the
diamagnetic state of the polymer with a singlet–triplet gap
wider than 1.37 eV
Formation of Hexagonal Fullerene Layers from Neutral and Negatively Charged Fullerenes in {(Ph<sub>3</sub>P)<sub>3</sub>Au<sup>+</sup>}<sub>2</sub>(C<sub>60</sub><sup>•–</sup>)<sub>2</sub>(C<sub>60</sub>)·C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> Containing Gold Cations with the <i>C</i><sub>3<i>v</i></sub> Symmetry
Fullerene
salt {(Ph<sub>3</sub>P)<sub>3</sub>Au<sup>+</sup>}<sub>2</sub>(C<sub>60</sub><sup>•–</sup>)<sub>2</sub>(C<sub>60</sub>)·C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (<b>1</b>) containing (Ph<sub>3</sub>P)<sub>3</sub>Au<sup>+</sup> cations
with the <i>C</i><sub>3<i>v</i></sub> symmetry
has been obtained as single crystals. Hexagonal
corrugated fullerene layers formed in <b>1</b> alternate with
the layers consisting of (Ph<sub>3</sub>P)<sub>3</sub>Au<sup>+</sup> and C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> along
the <i>c</i> axis. According to IR spectra and peculiarities
of the crystal structure, the charge on fullerenes in the layers is
evaluated to be −1 for two and close to zero for one C<sub>60</sub>. These fullerenes have different cationic surroundings,
and positively charged gold atoms approach closer to C<sub>60</sub><sup>•–</sup>. Charged and neutral fullerenes are closely
packed within hexagonal layers with an interfullerene center-to-center
distance of 10.02 Å and multiple short van der Waals C···C
contacts. The distances between C<sub>60</sub><sup>•–</sup> are essentially longer with an interfullerene center-to-center distance
of 10.37 Å due to corrugation of the layers, and no van der Waals
contacts are formed in this case. As a result, each C<sub>60</sub><sup>•–</sup> has only three negatively charged fullerene
neighbors with rather long interfullerene distances providing only
weak antiferromagnetic interaction of spins in the fullerene layers
with a Weiss temperature of −5 K
Synthesis, Structural and Magnetic Properties of Ternary Complexes of (Me<sub>4</sub>P<sup>+</sup>)·{[Fe(I)Pc(−2)]<sup>−</sup>}·Triptycene and (Me<sub>4</sub>P<sup>+</sup>)·{[Fe(I)Pc(−2)]<sup>−</sup>}·(<i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′‑Tetrabenzyl‑<i>p</i>‑phenylenediamine)<sub>0.5</sub> with Iron(I) Phthalocyanine Anions
Ternary complexes
of (Me<sub>4</sub>P<sup>+</sup>)·{[Fe(I)Pc(−2)]<sup>−</sup>}·TPC (<b>1</b>) and (Me<sub>4</sub>P<sup>+</sup>)·{[Fe(I)Pc(−2)]<sup>−</sup>}·(TBPDA)<sub>0.5</sub> (<b>2</b>) containing iron(I) phthalocyanine anions,
tetramethylphosphonium cations (Me<sub>4</sub>P<sup>+</sup>), and
neutral structure-forming triptycene (TPC) or <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetrabenzyl-<i>p</i>-phenylenediamine (TBPDA) molecules have been obtained
as single crystals. In contrast to previously studied ionic compounds
with monomeric [(Fe(I)Pc(−2)]<sup>−</sup> anions, the
anions form coordination {[Fe(I)Pc(−2)]<sup>−</sup>}<sub>2</sub> dimers both in <b>1</b> and <b>2</b>, in which
a nitrogen atom of one phthalocyanine anion weakly coordinates to
the iron(I) atom of neighboring [Fe(I)Pc(−2)]<sup>−</sup>. The Fe···N distances in the dimers are 3.08(1) and
3.12(1) Å in <b>1</b> at 280 K and 2.986(5) (100 K) and
3.011(5) Å (180 K) in <b>2</b>. The {[Fe(I)Pc(−2)]<sup>−</sup>}<sub>2</sub> dimers are packed in the layers in <b>1</b> arranged parallel to the <i>ac</i> plane and in
isolated chains in <b>2</b> arranged along the <i>a</i> axis. Extended Hückel based calculation of intermolecular
overlap integrals showed stronger and weaker π–π
interactions within and between phthalocyanine dimers, respectively,
both in <b>1</b> and <b>2</b>. EPR signals of both complexes
manifest two components. An major low-field asymmetric component is
attributed to the Fe(I) atoms with the d<sup>7</sup> configuration.
An origin minor narrow signal with <i>g</i>-factor close
to the free-electron value (<i>g</i> = 2.0018–2.0035)
is assigned to partial electron density transfer from the iron(I)
center to the phthalocyanine macrocycle and the formation of the [Fe(II)Pc(−3)]<sup>−</sup> species. Effective magnetic moments of the complexes
of 1.69 (<b>1</b>) and 1.76 μ<sub>B</sub> (<b>2</b>) correspond to the contribution of about one <i>S</i> = <sup>1</sup>/<sub>2</sub> spin per formula unit in accordance with low-spin
state of [Fe(I)Pc(−2)]<sup>−</sup>. Negative Weiss temperatures
of −7.6 K (<b>1</b>) and −13 K (<b>2</b>) in the 30–300 K range indicate antiferromagnetic interaction
of spins in the phthalocyanine dimers. The multicomponent approach
was previously proposed for the anionic fullerene complex formation.
It also seems very promising to design and synthesize anionic phthalocyanine
complexes with one- and two-dimensional macrocycle arrangements
Molecular Design of Anionic Phthalocyanines with π–π Stacking Columnar Arrangement. Crystal Structures, Optical, and Magnetic Properties of Salts with the Iron(I) Hexadecachlorophthalocyanine Anions
Ionic
compounds containing iron(I) hexadecachlorophthalocyanine
anions have been obtained for the first time as single crystals: (PPN<sup>+</sup>){[Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup>}
(<b>1</b>), (Ph<sub>3</sub>MeP<sup>+</sup>)<sub>2</sub>{[Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup>}(Br<sup>–</sup>)·C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (<b>2</b>), and (PPN<sup>+</sup>)<sub>2</sub>[Fe(I, II)Cl<sub>16</sub>Pc(−2)]<sub>3</sub><sup>(2−)</sup>·4C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (<b>3</b>), where PPN<sup>+</sup> is the cation of bis(triphenylphosphoranylidene)ammonium
and Ph<sub>3</sub>MeP<sup>+</sup> is the triphenylmethylphosphonium
cation. The [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup> anions form closely packed π–π stacking columns
in <b>1</b>–<b>3</b>. Salts <b>1</b> and <b>2</b> with integer −1 charge on iron phthalocyanines have
uniform and weakly dimerized columns, respectively. Salt <b>3</b> has two cations per three iron phthalocyanine molecules which are
arranged in trimers within the columns. Different shift of phthalocyanines
at the same interplanar distances of 3.33–3.38 Å provides
essentially shorter Fe···Fe distances in <b>3</b> (3.62–3.84 Å) than those in <b>1</b> and <b>2</b> (5.07–5.45 Å). Calculations show a strong LUMO–LUMO
overlapping between [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup> in <b>1</b>–<b>3</b> with the overlap integrals
of 4.1–7.6 × 10<sup>–3</sup>. Weak signals attributed
to the [Fe(II)Cl<sub>16</sub>Pc(−3)]<sup>−</sup> species
with the delocalization of electron on the phthalocyanine macrocycles
are observed in the EPR spectra of <b>1</b>–<b>3</b>. The content of this admixture is less than 1% in all salts. Nevertheless,
static magnetic susceptibility measurements for <b>3</b> detected
significant magnetization. The effective magnetic moment is 4.05 μ<sub>B</sub> per formula unit at 300 K. It can originate from the spins
localized on the iron atoms of [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup>. The Weiss temperature of −53 K in the 60–300
K range indicates a strong antiferromagnetic interaction of spins
which results in the decreases of magnetic moment of <b>3</b> with temperature below 220 K down to 2.72 μ<sub>B</sub> at
6 K. Optical spectra of <b>1</b>–<b>3</b> show
bands ascribed to [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup> at 339–349, 538–548, 685–691, and 805–821
nm. The bands in the NIR range at 1740–1810 nm were attributed
to charge transfer excitations within phthalocyanine columns associated
with the unpaired electrons on the iron atoms
Negatively Charged Iron-Bridged Fullerene Dimer {Fe(CO)<sub>2</sub>‑μ<sub>2</sub>‑η<sup>2</sup>,η<sup>2</sup>‑C<sub>60</sub>}<sub>2</sub><sup>2–</sup>
The interaction of {Cryptand(K+)}(C60•–) with Fe3(CO)12 produced
{Cryptand(K+)}2{Fe(CO)2-μ2-η2,η2-C60}22–·2.5C6H4Cl2 (1) as the first
negatively charged iron-bridged fullerene C60 dimer. The
bridged iron atoms are coordinated to two 6–6 bonds of one
C60 hexagon with short and long C(C60)–Fe
bonds with average lengths of 2.042(3) and 2.088(3) Å. Fullerenes
are close to each other in the dimer with a center-to-center interfullerene
distance of 10.02 Å. Optical spectra support the localization
of negative electron density on the Fe2(CO)4 units, which causes a 50 cm–1 shift of the CO
vibration bands to smaller wavenumbers, and the C60 cages.
Dimers are diamagnetic and electron paramagnetic resonance silent
and have a singlet ground state resulting from the formation of an
Fe–Fe bond in the dimer with a length of 2.978(4) Å. According
to density functional theory calculations, the excited triplet state
is higher than the ground state by 6.5 kcal/mol. Compound 1 shows a broad near-infrared band with a maximum at 970 nm, which
is attributable to the charge transfer from the orbitals localized
mainly on iron atoms to the C60 ligand
Molecular Design of Anionic Phthalocyanines with π–π Stacking Columnar Arrangement. Crystal Structures, Optical, and Magnetic Properties of Salts with the Iron(I) Hexadecachlorophthalocyanine Anions
Ionic
compounds containing iron(I) hexadecachlorophthalocyanine
anions have been obtained for the first time as single crystals: (PPN<sup>+</sup>){[Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup>}
(<b>1</b>), (Ph<sub>3</sub>MeP<sup>+</sup>)<sub>2</sub>{[Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup>}(Br<sup>–</sup>)·C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (<b>2</b>), and (PPN<sup>+</sup>)<sub>2</sub>[Fe(I, II)Cl<sub>16</sub>Pc(−2)]<sub>3</sub><sup>(2−)</sup>·4C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (<b>3</b>), where PPN<sup>+</sup> is the cation of bis(triphenylphosphoranylidene)ammonium
and Ph<sub>3</sub>MeP<sup>+</sup> is the triphenylmethylphosphonium
cation. The [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup> anions form closely packed π–π stacking columns
in <b>1</b>–<b>3</b>. Salts <b>1</b> and <b>2</b> with integer −1 charge on iron phthalocyanines have
uniform and weakly dimerized columns, respectively. Salt <b>3</b> has two cations per three iron phthalocyanine molecules which are
arranged in trimers within the columns. Different shift of phthalocyanines
at the same interplanar distances of 3.33–3.38 Å provides
essentially shorter Fe···Fe distances in <b>3</b> (3.62–3.84 Å) than those in <b>1</b> and <b>2</b> (5.07–5.45 Å). Calculations show a strong LUMO–LUMO
overlapping between [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup> in <b>1</b>–<b>3</b> with the overlap integrals
of 4.1–7.6 × 10<sup>–3</sup>. Weak signals attributed
to the [Fe(II)Cl<sub>16</sub>Pc(−3)]<sup>−</sup> species
with the delocalization of electron on the phthalocyanine macrocycles
are observed in the EPR spectra of <b>1</b>–<b>3</b>. The content of this admixture is less than 1% in all salts. Nevertheless,
static magnetic susceptibility measurements for <b>3</b> detected
significant magnetization. The effective magnetic moment is 4.05 μ<sub>B</sub> per formula unit at 300 K. It can originate from the spins
localized on the iron atoms of [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup>. The Weiss temperature of −53 K in the 60–300
K range indicates a strong antiferromagnetic interaction of spins
which results in the decreases of magnetic moment of <b>3</b> with temperature below 220 K down to 2.72 μ<sub>B</sub> at
6 K. Optical spectra of <b>1</b>–<b>3</b> show
bands ascribed to [Fe(I)Cl<sub>16</sub>Pc(−2)]<sup>−</sup> at 339–349, 538–548, 685–691, and 805–821
nm. The bands in the NIR range at 1740–1810 nm were attributed
to charge transfer excitations within phthalocyanine columns associated
with the unpaired electrons on the iron atoms
Magnetic and Optical Properties of Layered (Me<sub>4</sub>P<sup>+</sup>)[M<sup>IV</sup>O(Pc<sup>•3–</sup>)]<sup>•–</sup>(TPC)<sub>0.5</sub>·C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> Salts (M = Ti and V) Composed of π‑Stacking Dimers of Titanyl and Vanadyl Phthalocyanine Radical Anions
Two isostructural
salts with radical anions of titanyl and vanadyl
phthalocyanines (Me<sub>4</sub>P<sup>+</sup>)[M<sup>IV</sup>O(Pc<sup>•3–</sup>)]<sup>•–</sup>(TPC)<sub>0.5</sub>·C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub> (M
= Ti (<b>1</b>), V (<b>2</b>)), where TPC is triptycene,
were obtained. These salts contain phthalocyanine layers composed
of the {[M<sup>IV</sup>O(Pc<sup>•3–</sup>)]<sup>•–</sup>}<sub>2</sub> dimers with strong π–π intradimer
interaction. The reduction of metal phthalocyanines was centered on
the Pc macrocycles providing the appearance of new bands in the near
infrared range and a blue shift of Q- and Soret bands. That results
in the alternation of shorter and longer C–N<sub>imine</sub> bonds in Pc<sup>•3–</sup>. Only one <i>S</i> = 1/2 spin is delocalized over Pc<sup>•3–</sup> in <b>1</b> providing a χ<sub>M</sub><i>T</i> value
of 0.364 emu K mol<sup>–1</sup> at 300 K. Salt <b>1</b> showed antiferromagnetic behavior approximated by the Heisenberg
model for isolated pairs of antiferromagnetically interacting spins
with exchange interaction of <i>J</i>/<i>k</i><sub>B</sub> = −123.0 K. The χ<sub>M</sub><i>T</i> value for <b>2</b> is equal to 0.617 emu K mol<sup>–1</sup> at 300 K to show the contribution of two <i>S</i> = 1/2
spins localized on V<sup>IV</sup> and delocalized over Pc<sup>•3–</sup>. Magnetic behavior of <b>2</b> is described by the Heisenberg
model for a four-spin system with strong intermolecular coupling between
Pc<sup>•3–</sup> in {[V<sup>IV</sup>O(Pc<sup>•3–</sup>)]<sup>•–</sup>}<sub>2</sub> (<i>J</i><sub>inter</sub>/<i>k</i><sub>B</sub> = −105.0 K) and
weaker intramolecular coupling between the V<sup>IV</sup> and Pc<sup>•3–</sup> (<i>J</i><sub>intra</sub>/<i>k</i><sub>B</sub> = −15.2 K)
Spin Crossover in Anionic Cobalt-Bridged Fullerene (Bu<sub>4</sub>N<sup>+</sup>){Co(Ph<sub>3</sub>P)}<sub>2</sub>(μ<sub>2</sub>‑Cl<sup>–</sup>)(μ<sub>2</sub>‑η<sup>2</sup>,η<sup>2</sup>‑C<sub>60</sub>)<sub>2</sub> Dimers
A spin crossover
phenomena is observed in an anionic (Bu<sub>4</sub>N<sup>+</sup>){Co(Ph<sub>3</sub>P)}<sub>2</sub>(μ<sub>2</sub>-Cl<sup>–</sup>)(μ<sub>2</sub>-η<sup>2</sup>,η<sup>2</sup>-C<sub>60</sub>)<sub>2</sub>·2C<sub>6</sub>H<sub>14</sub> (<b>1</b>) complex
in which two cobalt atoms bridge two fullerene
molecules to form a dimer. The dimer has a triplet ground state with
two weakly coupling Co<sup>0</sup> atoms (<i>S</i> = 1/2).
The spin transition realized above 150 K is accompanied by a cobalt-to-fullerene
charge transfer that forms a quintet excited state with a high spin
Co<sup>I</sup> (<i>S</i> = 1) and C<sub>60</sub><sup>•–</sup> (<i>S</i> = 1/2)