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Structure and assembly mechanism of a centipede-shaped high-nuclear Dy14Cu12 heterometallic nanocluster.
- Source :
- CrystEngComm; 1/7/2023, Vol. 25 Issue 1, p114-121, 8p
- Publication Year :
- 2023
-
Abstract
- The assembly studies of high-nuclear clusters have received much interest in recent years due to their targeted synthesis for some special usages. A Schiff base ligand 2-[N-(2-hydroxynaphthylidene)amino]-2-(hydroxymethyl)propane-1,3-diol (H<subscript>4</subscript>L) was thus prepared in this work and was allowed to react with [Cu<subscript>2</subscript>(OAc)<subscript>4</subscript>(H<subscript>2</subscript>O)<subscript>2</subscript>] and Dy(NO)<subscript>3</subscript>·6H<subscript>2</subscript>O, giving a high-nuclear 3d–4f heterometallic Cu<subscript>12</subscript>Dy<subscript>14</subscript> nanocluster (1) with the formula [(C<subscript>2</subscript>H<subscript>5</subscript>)<subscript>3</subscript>NH]<subscript>4</subscript>[Cu<subscript>12</subscript>Dy<subscript>14</subscript>O(OH)<subscript>16</subscript>(H<subscript>2</subscript>L)<subscript>8</subscript>(HL)<subscript>4</subscript>(HL′)<subscript>4</subscript>(OAc)<subscript>10</subscript>](NO<subscript>3</subscript>)<subscript>4</subscript>(OAc)<subscript>2</subscript>·6CH<subscript>3</subscript>CN·5EtOH·1.5H<subscript>2</subscript>O (H<subscript>3</subscript>L′ = 1,1,1-tris-(hydroxymethyl)methanamine). It features a centipede-shaped structure constructed from eight Dy<subscript>3</subscript>Cu cubanes sharing the Dy(III) vertices. Its assembly mechanism was explored through time-dependent high-resolution electrospray ionization mass spectrometry (HRESI-MS). This revealed that the hierarchical assembly of 1 undergoes two possible routes: H<subscript>4</subscript>L → DyCuL → Dy<subscript>2</subscript>CuL → Dy<subscript>3</subscript>Cu<subscript>2</subscript>L<subscript>2</subscript> → Dy<subscript>4</subscript>Cu<subscript>2</subscript>L<subscript>2</subscript> → Dy<subscript>4</subscript>Cu<subscript>3</subscript>L<subscript>3</subscript> → Dy<subscript>5</subscript>Cu<subscript>4</subscript>L<subscript>4</subscript>→ Dy<subscript>14</subscript>Cu<subscript>12</subscript>L<subscript>12</subscript>L′<subscript>4</subscript> and H<subscript>4</subscript>L → DyCuL → DyCu<subscript>2</subscript>L → Dy<subscript>2</subscript>Cu<subscript>2</subscript>L<subscript>2</subscript> → Dy<subscript>2</subscript>Cu<subscript>3</subscript>L<subscript>4</subscript> → Dy<subscript>3</subscript>Cu<subscript>4</subscript>L<subscript>4</subscript> → Dy<subscript>5</subscript>Cu<subscript>4</subscript>L<subscript>4</subscript> → Dy<subscript>14</subscript>Cu<subscript>12</subscript>L<subscript>12</subscript>L′<subscript>4</subscript>. These results not only provide solid evidence for understanding the assembly mechanism of high-nuclear 3d–4f clusters, but also help to give some hints for designing and preparing new high-nuclear clusters. [ABSTRACT FROM AUTHOR]
- Subjects :
- ELECTROSPRAY ionization mass spectrometry
COPPER
NITROSYL compounds
SCHIFF bases
Subjects
Details
- Language :
- English
- ISSN :
- 14668033
- Volume :
- 25
- Issue :
- 1
- Database :
- Complementary Index
- Journal :
- CrystEngComm
- Publication Type :
- Academic Journal
- Accession number :
- 160870522
- Full Text :
- https://doi.org/10.1039/d2ce01291j