Competing Intermolecular and Molecule-Surface Interactions: Dipole-Dipole-Driven Patterns in Mixed Carborane Self-Assembled Monolayers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00584549" target="_blank" >RIV/61388955:_____/24:00584549 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/68378271:_____/24:00584549 RIV/61388980:_____/24:00584549 RIV/00216208:11320/24:10479454

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.chemmater.3c03210" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.chemmater.3c03210</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.chemmater.3c03210" target="_blank" >10.1021/acs.chemmater.3c03210</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Competing Intermolecular and Molecule-Surface Interactions: Dipole-Dipole-Driven Patterns in Mixed Carborane Self-Assembled Monolayers

Popis výsledku v původním jazyce

Carboranedithiol isomers adsorbing with opposite orientations of their dipoles on surfaces are self-assembled together to form mixed monolayers where both lateral dipole-dipole and lateral thiol-thiolate (S-H···S) interactions provide enhanced stability over single-component monolayers. We demonstrate the first instance of the ability to map individual isomers in a mixed monolayer using the model system carboranedithiols on Au{111}. The addition of methyl groups to one isomer provides both an enhanced dipole moment and extra apparent height for differentiation via scanning tunneling microscopy (STM). Associated computational investigations rationalize favorable interactions of mixed pairs and the associated stability changes that arise from these interactions. Both STM images and Monte Carlo simulations yield similarly structured mixed monolayers, where approximately 10% of the molecules have reversed dipole moment orientations but no direct chemical attachment to the surface, leading to homogeneous monolayers with no apparent phase separation. Deprotonating the thiols by depositing the molecules under basic conditions eliminates the lateral S-H···S interactions while accentuating the dipole-dipole forces. The molecular system investigated is composed of isomeric molecules with opposite orientations of dipoles and identical surface packing, which enables the mapping of individual molecules within the mixed monolayers and enables analyses of the contributions of the relatively weak lateral interactions to the overall stability of the assemblies.

Název v anglickém jazyce

Competing Intermolecular and Molecule-Surface Interactions: Dipole-Dipole-Driven Patterns in Mixed Carborane Self-Assembled Monolayers

Popis výsledku anglicky

Carboranedithiol isomers adsorbing with opposite orientations of their dipoles on surfaces are self-assembled together to form mixed monolayers where both lateral dipole-dipole and lateral thiol-thiolate (S-H···S) interactions provide enhanced stability over single-component monolayers. We demonstrate the first instance of the ability to map individual isomers in a mixed monolayer using the model system carboranedithiols on Au{111}. The addition of methyl groups to one isomer provides both an enhanced dipole moment and extra apparent height for differentiation via scanning tunneling microscopy (STM). Associated computational investigations rationalize favorable interactions of mixed pairs and the associated stability changes that arise from these interactions. Both STM images and Monte Carlo simulations yield similarly structured mixed monolayers, where approximately 10% of the molecules have reversed dipole moment orientations but no direct chemical attachment to the surface, leading to homogeneous monolayers with no apparent phase separation. Deprotonating the thiols by depositing the molecules under basic conditions eliminates the lateral S-H···S interactions while accentuating the dipole-dipole forces. The molecular system investigated is composed of isomeric molecules with opposite orientations of dipoles and identical surface packing, which enables the mapping of individual molecules within the mixed monolayers and enables analyses of the contributions of the relatively weak lateral interactions to the overall stability of the assemblies.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry of Materials

ISSN

0897-4756

e-ISSN

1520-5002

Svazek periodika

36

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

2085-2095

Kód UT WoS článku

001166534100001

EID výsledku v databázi Scopus

2-s2.0-85186165727