Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks

Naveen Kumar Allampally, Maria Jose Mayoral, Sarayute Chansai, Maria Cristina Lagunas, Christopher Hardacre, Vladimir Stepanenko, Rodrigo Q. Albuquerque, Gustavo Fern‚ndez

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

We report the self-assembly of a new family of hydrophobic,bis(pyridyl) PtII complexes featuring an extendedoligophenyleneethynylene-derived π-surface appended withsix long (dodecyloxy (2)) or short (methoxy (3)) side groups.Complex 2, containing dodecyloxy chains, forms fibrous assemblies with a slipped arrangement of the monomer units (dPt···Pt… =14 Å) in both nonpolar solvents and the solid state.Dispersion-corrected PM6 calculations suggest that this organizationis driven by cooperative π–π, C-H···Cl and π–Pt interactions, which is supported by EXAFS and 2D NMR spectroscopic analysis. In contrast, nearly parallel π-stacks (dPt···Pt… = 4.4 Å) stabilized by multiple π–π and C-H···Cl contact sare obtained in the crystalline state for 3 lacking longside chains, as shown by X-ray analysis and PM6 calculations.Our results reveal not only the key role of alkyl chain lengthin controlling self-assembly modes but also show the relevanceof Pt-bound chlorine ligands as new supramolecular synthons.
Original languageEnglish
Pages (from-to)7810-7816
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number23
Early online date26 Apr 2016
DOIs
Publication statusPublished - 01 Jun 2016

Fingerprint

Self assembly
Spectroscopic analysis
Chlorine
X ray analysis
Monomers
Ligands
Nuclear magnetic resonance
Crystalline materials

Cite this

Allampally, Naveen Kumar ; Mayoral, Maria Jose ; Chansai, Sarayute ; Lagunas, Maria Cristina ; Hardacre, Christopher ; Stepanenko, Vladimir ; Albuquerque, Rodrigo Q. ; Fern‚ndez, Gustavo . / Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 23. pp. 7810-7816.
@article{3324b596a1354d0688289519d7c32a05,
title = "Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks",
abstract = "We report the self-assembly of a new family of hydrophobic,bis(pyridyl) PtII complexes featuring an extendedoligophenyleneethynylene-derived π-surface appended withsix long (dodecyloxy (2)) or short (methoxy (3)) side groups.Complex 2, containing dodecyloxy chains, forms fibrous assemblies with a slipped arrangement of the monomer units (dPt···Pt… =14 {\AA}) in both nonpolar solvents and the solid state.Dispersion-corrected PM6 calculations suggest that this organizationis driven by cooperative π–π, C-H···Cl and π–Pt interactions, which is supported by EXAFS and 2D NMR spectroscopic analysis. In contrast, nearly parallel π-stacks (dPt···Pt… = 4.4 {\AA}) stabilized by multiple π–π and C-H···Cl contact sare obtained in the crystalline state for 3 lacking longside chains, as shown by X-ray analysis and PM6 calculations.Our results reveal not only the key role of alkyl chain lengthin controlling self-assembly modes but also show the relevanceof Pt-bound chlorine ligands as new supramolecular synthons.",
author = "Allampally, {Naveen Kumar} and Mayoral, {Maria Jose} and Sarayute Chansai and Lagunas, {Maria Cristina} and Christopher Hardacre and Vladimir Stepanenko and Albuquerque, {Rodrigo Q.} and Gustavo Fern‚ndez",
year = "2016",
month = "6",
day = "1",
doi = "10.1002/chem.201600176",
language = "English",
volume = "22",
pages = "7810--7816",
journal = "Chemistry-a European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "23",

}

Allampally, NK, Mayoral, MJ, Chansai, S, Lagunas, MC, Hardacre, C, Stepanenko, V, Albuquerque, RQ & Fern‚ndez, G 2016, 'Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks', Chemistry - A European Journal, vol. 22, no. 23, pp. 7810-7816. https://doi.org/10.1002/chem.201600176

Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks. / Allampally, Naveen Kumar ; Mayoral, Maria Jose; Chansai, Sarayute; Lagunas, Maria Cristina; Hardacre, Christopher; Stepanenko, Vladimir ; Albuquerque, Rodrigo Q. ; Fern‚ndez, Gustavo .

In: Chemistry - A European Journal, Vol. 22, No. 23, 01.06.2016, p. 7810-7816.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Control over the Self-Assembly Modes of PtII Complexes by Alkyl Chain Variation: From Slipped to Parallel π-Stacks

AU - Allampally, Naveen Kumar

AU - Mayoral, Maria Jose

AU - Chansai, Sarayute

AU - Lagunas, Maria Cristina

AU - Hardacre, Christopher

AU - Stepanenko, Vladimir

AU - Albuquerque, Rodrigo Q.

AU - Fern‚ndez, Gustavo

PY - 2016/6/1

Y1 - 2016/6/1

N2 - We report the self-assembly of a new family of hydrophobic,bis(pyridyl) PtII complexes featuring an extendedoligophenyleneethynylene-derived π-surface appended withsix long (dodecyloxy (2)) or short (methoxy (3)) side groups.Complex 2, containing dodecyloxy chains, forms fibrous assemblies with a slipped arrangement of the monomer units (dPt···Pt… =14 Å) in both nonpolar solvents and the solid state.Dispersion-corrected PM6 calculations suggest that this organizationis driven by cooperative π–π, C-H···Cl and π–Pt interactions, which is supported by EXAFS and 2D NMR spectroscopic analysis. In contrast, nearly parallel π-stacks (dPt···Pt… = 4.4 Å) stabilized by multiple π–π and C-H···Cl contact sare obtained in the crystalline state for 3 lacking longside chains, as shown by X-ray analysis and PM6 calculations.Our results reveal not only the key role of alkyl chain lengthin controlling self-assembly modes but also show the relevanceof Pt-bound chlorine ligands as new supramolecular synthons.

AB - We report the self-assembly of a new family of hydrophobic,bis(pyridyl) PtII complexes featuring an extendedoligophenyleneethynylene-derived π-surface appended withsix long (dodecyloxy (2)) or short (methoxy (3)) side groups.Complex 2, containing dodecyloxy chains, forms fibrous assemblies with a slipped arrangement of the monomer units (dPt···Pt… =14 Å) in both nonpolar solvents and the solid state.Dispersion-corrected PM6 calculations suggest that this organizationis driven by cooperative π–π, C-H···Cl and π–Pt interactions, which is supported by EXAFS and 2D NMR spectroscopic analysis. In contrast, nearly parallel π-stacks (dPt···Pt… = 4.4 Å) stabilized by multiple π–π and C-H···Cl contact sare obtained in the crystalline state for 3 lacking longside chains, as shown by X-ray analysis and PM6 calculations.Our results reveal not only the key role of alkyl chain lengthin controlling self-assembly modes but also show the relevanceof Pt-bound chlorine ligands as new supramolecular synthons.

U2 - 10.1002/chem.201600176

DO - 10.1002/chem.201600176

M3 - Article

VL - 22

SP - 7810

EP - 7816

JO - Chemistry-a European Journal

JF - Chemistry-a European Journal

SN - 0947-6539

IS - 23

ER -