Highly Symmetrical Palladium Cluster Complexes with Either Anticuboctahedral or Cuboctahedral Pd<sub>13</sub> Core: Theoretical Insight into Factors Determining Symmetrical Structure

One of the important open questions is what factor(s) determines the symmetry of the structure of the metal nanocluster complex. [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> (<b>Anti-μ</b><sub><b>4</b></sub>; C<sub>16</sub>H<sub>16</sub> = [2.2]paracyclophane) has an anticuboctahedral Pd<sub>13</sub> core unlike [Pd<sub>13</sub>(μ<sub>4</sub>-C<sub>7</sub>H<sub>7</sub>)<sub>6</sub>]<sup>2+</sup> with cuboctahedral Pd<sub>13</sub> core. DFT calculations show that <b>Anti-μ</b><sub><b>4</b></sub> is more stable than isomers, [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>3</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>]<sup>+</sup> and [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>2</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>]<sup>+</sup> with cuboctahedral Pd<sub>13</sub> core (<b>Cubo-μ</b><sub><b>3</b></sub><b>,μ</b><sub><b>4</b></sub> and <b>Cubo-μ</b><sub><b>2</b></sub><b>,μ</b><sub><b>4</b></sub>, respectively) and [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>3</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> with distorted icosahedral Pd<sub>13</sub> core (<b>dis-Ih-μ</b><sub><b>3</b></sub>). Not the stabilities of [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>]<sup>+</sup> core and (C<sub>16</sub>H<sub>16</sub>)<sub>6</sub> ligand-shell but rather the interaction energy (<i>E</i><sub>int</sub>) between [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>]<sup>+</sup> and (C<sub>16</sub>H<sub>16</sub>)<sub>6</sub> ligand-shell determines stabilities of these complexes. μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub> coordination bond is stronger than μ<sub>2</sub>- and μ<sub>3</sub>-coordination bonds, leading to a larger <i>E</i><sub>int</sub> value in <b>Anti-μ</b><sub><b>4</b></sub> than in isomers bearing μ<sub>2</sub>- or μ<sub>3</sub>-coordination bond. An icosahedral Pd<sub>13</sub> core is not favorable for these Pd<sub>13</sub> complexes because of the absence of a Pd<sub>4</sub> plane. [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> with cuboctahedral Pd<sub>13</sub> (<b>Cubo-μ</b><sub><b>4</b></sub>) is not stable despite the presence of six Pd<sub>4</sub> planes, because its three Pd<sub>4</sub> planes with μ-Cl ligand cannot form μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub> coordination bond due to steric repulsion of C<sub>16</sub>H<sub>16</sub> with the μ-Cl ligand. In contrast, <b>Anti-μ</b><sub><b>4</b></sub> is stable because it has six Pd<sub>4</sub> planes with no Cl ligand to form strong μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub> coordination bonds without steric repulsion. Also, discussion is presented on the difference in symmetry between [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> and [Pd<sub>13</sub>(μ<sub>4</sub>-C<sub>7</sub>H<sub>7</sub>)<sub>6</sub>]<sup>2+</sup>.

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Journal
The Journal of Physical Chemistry A
Published
2025-02-26
DOI
https://doi.org/10.1021/acs.jpca.4c07401
Primary Topic
Nanocluster Synthesis and Applications
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article
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article

Highly Symmetrical Palladium Cluster Complexes with Either Anticuboctahedral or Cuboctahedral Pd13 Core: Theoretical Insight into Factors Determining Symmetrical Structure

Shigeyoshi Sakaki, Tetsuro Murahashi, Yu Tian, Bo Zhu
The Journal of Physical Chemistry A
Nanocluster Synthesis and Applications
article

Highly Symmetrical Palladium Cluster Complexes with Either Anticuboctahedral or Cuboctahedral Pd13 Core: Theoretical Insight into Factors Determining Symmetrical Structure

Shigeyoshi Sakaki, Tetsuro Murahashi, Yu Tian, Bo Zhu
article en

Abstract

One of the important open questions is what factor(s) determines the symmetry of the structure of the metal nanocluster complex. [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> (<b>Anti-μ</b><sub><b>4</b></sub>; C<sub>16</sub>H<sub>16</sub> = [2.2]paracyclophane) has an anticuboctahedral Pd<sub>13</sub> core unlike [Pd<sub>13</sub>(μ<sub>4</sub>-C<sub>7</sub>H<sub>7</sub>)<sub>6</sub>]<sup>2+</sup> with cuboctahedral Pd<sub>13</sub> core. DFT calculations show that <b>Anti-μ</b><sub><b>4</b></sub> is more stable than isomers, [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>3</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>]<sup>+</sup> and [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>2</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>3</sub>]<sup>+</sup> with cuboctahedral Pd<sub>13</sub> core (<b>Cubo-μ</b><sub><b>3</b></sub><b>,μ</b><sub><b>4</b></sub> and <b>Cubo-μ</b><sub><b>2</b></sub><b>,μ</b><sub><b>4</b></sub>, respectively) and [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>3</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> with distorted icosahedral Pd<sub>13</sub> core (<b>dis-Ih-μ</b><sub><b>3</b></sub>). Not the stabilities of [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>]<sup>+</sup> core and (C<sub>16</sub>H<sub>16</sub>)<sub>6</sub> ligand-shell but rather the interaction energy (<i>E</i><sub>int</sub>) between [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>]<sup>+</sup> and (C<sub>16</sub>H<sub>16</sub>)<sub>6</sub> ligand-shell determines stabilities of these complexes. μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub> coordination bond is stronger than μ<sub>2</sub>- and μ<sub>3</sub>-coordination bonds, leading to a larger <i>E</i><sub>int</sub> value in <b>Anti-μ</b><sub><b>4</b></sub> than in isomers bearing μ<sub>2</sub>- or μ<sub>3</sub>-coordination bond. An icosahedral Pd<sub>13</sub> core is not favorable for these Pd<sub>13</sub> complexes because of the absence of a Pd<sub>4</sub> plane. [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> with cuboctahedral Pd<sub>13</sub> (<b>Cubo-μ</b><sub><b>4</b></sub>) is not stable despite the presence of six Pd<sub>4</sub> planes, because its three Pd<sub>4</sub> planes with μ-Cl ligand cannot form μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub> coordination bond due to steric repulsion of C<sub>16</sub>H<sub>16</sub> with the μ-Cl ligand. In contrast, <b>Anti-μ</b><sub><b>4</b></sub> is stable because it has six Pd<sub>4</sub> planes with no Cl ligand to form strong μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub> coordination bonds without steric repulsion. Also, discussion is presented on the difference in symmetry between [Pd<sub>13</sub>(μ-Cl)<sub>3</sub>(μ<sub>4</sub>-C<sub>16</sub>H<sub>16</sub>)<sub>6</sub>]<sup>+</sup> and [Pd<sub>13</sub>(μ<sub>4</sub>-C<sub>7</sub>H<sub>7</sub>)<sub>6</sub>]<sup>2+</sup>.

The Journal of Physical Chemistry AVol. 129(10)
Northeast Normal University (CN), Jilin University (CN), Kyoto University (JP), Institute of Molecular Functional Materials (CN), Institute of Theoretical Physics (CN), Jilin Medical University (CN), Kyoto Katsura Hospital (JP), Institute of Science Tokyo (JP)
National Natural Science Foundation of China, Mitsubishi Foundation, Japan Society for the Promotion of Science, Core Research for Evolutional Science and Technology
Openalex Percentile: Top 98%
Nanocluster Synthesis and Applications
DOISourceOpenAlex
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