Organometallic Chemistry Tools for Building Biologically Relevant Nanoscale Systems DOI
James A. R. Tilden, Evan A. Doud, Hayden R. Montgomery

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

The recent emergence of organometallic chemistry for modification biomolecular nanostructures has begun to rewrite the long-standing assumption among practitioners that small-molecule organometallics are fundamentally incompatible with biological systems. This Perspective sets out clarify some existing misconceptions by focusing on growing toolbox modification. Specifically, we highlight key transformations in constructing complex biologically relevant systems nanomolecular scale, and synthesis hybrid nanomaterials composed classical nanomaterial components combined species. As research progresses, many challenges associated applying this context rapidly being reassessed. Looking future, utility will likely make them more ubiquitous construction nanostructures.

Language: Английский

Site-specific substitution in atomically precise carboranethiol-protected nanoclusters and concomitant changes in electronic properties DOI Creative Commons
Vivek Yadav, Arijit Jana,

Swetashree Acharya

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 30, 2025

We report the synthesis of [Ag17(o1-CBT)12]3- abbreviated as Ag17, a stable 8e⁻ anionic cluster with unique Ag@Ag12@Ag4 core-shell structure, where o1-CBT is ortho-carborane-1-thiol. By substituting Ag atoms Au and/or Cu at specific sites we created isostructural clusters [AuAg16(o1-CBT)12]3- (AuAg16), [Ag13Cu4(o1-CBT)12]3- (Ag13Cu4) and [AuAg12Cu4(o1-CBT)12]3- (AuAg12Cu4). These substitutions make systematic modulation their structural electronic properties. show that preferentially occupies core, while localizes in tetrahedral shell, influencing stability diversity clusters. The band gap expands systematically (2.09 eV for Ag17 to 2.28 AuAg12Cu4), altering optical absorption emission. Ultrafast measurements reveal longer excited-state lifetimes Cu-containing clusters, highlighting effect heteroatom incorporation. results demonstrate tunable platform designing nanoclusters tailored properties, implications optoelectronics catalysis. Tuning structure composition atomically precise metal leads property changes which, however, are still poorly understood. Here, authors synthesize precisely substituted analogues study luminescence

Language: Английский

Citations

2
Macrocyclic meta-Carborane Hexamer. Evaluation of Aromatic Characteristics As a Cluster-Based Analog to Phenyl-Bridged Macrocyclic Structures DOI
Peter L. Rodríguez‐Kessler, Alvaro Muñoz‐Castro

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Envisaging cluster-based aggregates of larger phenyl-bridged macrocyclic structures enables evaluation resemblance and differences between planar- spherical building blocks towards novel synthetic target architectures for molecular materials.

Language: Английский

Citations

1
Effect of Fluorinated Substitution on the Properties of Phenylethylamine Derivatives: A Density Functional Theory Study DOI
Yaping Tao,

Qirong Jiang,

Xinhui Zhang

et al.

Russian Journal of General Chemistry, Journal Year: 2025, Volume and Issue: 95(5), P. 1104 - 1116

Published: May 1, 2025

Language: Английский

Citations

0
Intercluster B-H and B-B Aggregation in iso- and trans-[B20H18]2-. Spherical Aromaticity in Borane Dimers DOI
Peter L. Rodríguez‐Kessler, Alvaro Muñoz‐Castro

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(33), P. 13960 - 13967

Published: Jan. 1, 2024

The formation of molecular-based functional materials is a key step towards the development technologies at nanoscale. Recently, it has been shown that after oxidation

Language: Английский

Citations

2
Counterion loss from charged surface-bound complexes drives the formation of loosely packed monolayers DOI Creative Commons

Christina Trang,

Carlos Mora Perez, Jingyi Ran

et al.

Published: May 29, 2024

The functionality of multicomponent self-assembled monolayers (SAMs) can be severely diminished by the segregation like components into nanoscale domains, a process that maximizes favorable short-range intermolecular interactions. Here, we explore use modular family sulfur-functionalized metal bis(terpyridine) complexes ([M(tpy-R)2]2+(PF6–)2) to prepare mixed SAMs, considering comparable structure, dimensions, and ionic composition these species should render them interchangeable within adsorbed surface layer. While voltammetry experiments show SAMs do exhibit compositions representative their assembly solutions, they also suggest, in line with previous reports, adjacent monolayer are separated gap ~1 nm. Remarkably, X-ray photoelectron spectroscopy studies reveal no F 1s peak features would confirm proliferation PF6− counterions on surface. We propose loose packed structure results from loss or exchange PF6– which introduces significant repulsive Coulomb interactions between 2+ charged complexes. hypothesis is supported an electrostatic model indicates form close if mobile present. First-principles calculations demonstrate complex-counterion binding weakened charge transfer gold substrate, suggesting this may play important role formation such low coverage SAMs. Together, study raises questions regarding assembly, organization, highlights new opportunities design assemblies free volume, for example, facilitate surface-based reactions support molecular switches.

Language: Английский

Citations

1
Counterion Loss from Charged Surface-Bound Complexes Drives the Formation of Loosely Packed Monolayers DOI Creative Commons

Christina D. M. Trang,

Carlos Mora Perez, Jingyi Ran

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25625 - 25639

Published: Sept. 9, 2024

The functionality of multicomponent self-assembled monolayers (SAMs) can be severely diminished by the segregation like components into nanoscale domains, a process that maximizes favorable short-range intermolecular interactions. Here, we explore use modular family sulfur-functionalized metal bis(terpyridine) complexes ([M(tpy-R)

Language: Английский

Citations

1
[o-C2B10H10]3 as a trimer aggregate of spherical aromatic carboranes. Persistence and interplay between spherical aromatic states DOI
Peter L. Rodríguez‐Kessler, Alvaro Muñoz‐Castro

Chemical Physics Letters, Journal Year: 2024, Volume and Issue: 858, P. 141752 - 141752

Published: Nov. 10, 2024

Language: Английский

Citations

1
Organometallic Chemistry Tools for Building Biologically Relevant Nanoscale Systems DOI
James A. R. Tilden, Evan A. Doud, Hayden R. Montgomery

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

The recent emergence of organometallic chemistry for modification biomolecular nanostructures has begun to rewrite the long-standing assumption among practitioners that small-molecule organometallics are fundamentally incompatible with biological systems. This Perspective sets out clarify some existing misconceptions by focusing on growing toolbox modification. Specifically, we highlight key transformations in constructing complex biologically relevant systems nanomolecular scale, and synthesis hybrid nanomaterials composed classical nanomaterial components combined species. As research progresses, many challenges associated applying this context rapidly being reassessed. Looking future, utility will likely make them more ubiquitous construction nanostructures.

Language: Английский

Citations

0