Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

Jack K. Clegg; Feng Li; Katrina A. Jolliffe; Leonard F. Lindoy; George V. Meehan; Simon Parsons; Peter A. Tasker; Fraser J. White

doi:10.1039/c3dt51531a

Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

Jack K. Clegg, Feng Li, Katrina A. Jolliffe, Leonard F. Lindoy^*, George V. Meehan, Simon Parsons, Peter A. Tasker, Fraser J. White

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

The sequential interaction of preformed [Cu₂(L¹11)₂(THF)₂] (where H₂L¹11 is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu₂(L⁴44)₂] · 2H₂O (where H₂L⁴44 is 1,1-(4,4'-oxybiphenylene)-bis(4,4-dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N'-dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di- and tetranuclear assemblies were obtained and their X-ray structures determined. Dinuclear [Cu₂(L¹11)₂(mpip)₂] · 2mpip incorporates two 5-coordinate, square pyramidal metal centres as does tetranuclear [{Cu₂(L¹11)₂}₂(dmpip)₂] · 2dmpip. In contrast, dinuclear [Cu₂(L¹11)₂(dmpip)₄] · dmpip and [{Cu₂(L¹11)₂}₂(thiomorph)₄] · 3thiomorph each contain two 5-coordinate and two 6-coordinate centres. Each of [Cu₂(L⁴44)₂(THF)₂] · 2THF and Cu₂(L⁴44)₂(mpip)₂] · H₂O incorporate only 5-coordinate metal centres, with the latter complex forming a one-dimensional hydrogen bonded ribbon-like structure directed along the crystallographic a-axis. In keeping with the documented tendency for the smallest, least strained assembly to form in supramolecular self-assembly processes, the incorporation of the flexible "oxy" linkage between the 4,4'-linked phenylene rings of H₂L³33 results in generation of a dinuclear [Cu₂L₂2] species rather than a trinuclear (triangular) [Cu₃L₃33] species of the type formed by the more rigid bis-beta-diketonato ligand analogue in which the biphenylene rings separating the β-diketone domains are directly coupled in their 4,4' positions.

Original language	English
Pages (from-to)	14315-14323
Number of pages	9
Journal	Dalton Transactions
Volume	42
Issue number	39
DOIs	https://doi.org/10.1039/c3dt51531a
Publication status	Published - 21 Oct 2013

Keywords / Materials (for Non-textual outputs)

SUPRAMOLECULAR CHEMISTRY
BIS(BETA-DIKETONATE) LIGANDS
MACROCYCLIC COMPLEXES
H-1-NMR SPECTROSCOPY
DIKETONATO LIGANDS
SOLVENT-EXTRACTION
CRYSTAL-STRUCTURES
BUILDING-BLOCKS
BETA-DIKETONES
ION CHEMISTRY

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10.1039/c3dt51531a

http://pubs.rsc.org/en/content/articlehtml/2013/dt/c3dt51531a

Pressure Sensitive Complexformation based on self assembling ligands
Parsons, S. (Principal Investigator), Jones, A. (Co-investigator), Kamenev, K. (Co-investigator) & Tasker, P. (Co-investigator)
EPSRC
1/03/09 → 29/08/12
Project: Research

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@article{7e44627cbd9443d0bde18a2e46042845,

title = "Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands",

abstract = "The sequential interaction of preformed [Cu2(L111)2(THF)2] (where H2L111 is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu2(L444)2] · 2H2O (where H2L444 is 1,1-(4,4'-oxybiphenylene)-bis(4,4-dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N'-dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di- and tetranuclear assemblies were obtained and their X-ray structures determined. Dinuclear [Cu2(L111)2(mpip)2] · 2mpip incorporates two 5-coordinate, square pyramidal metal centres as does tetranuclear [{Cu2(L111)2}2(dmpip)2] · 2dmpip. In contrast, dinuclear [Cu2(L111)2(dmpip)4] · dmpip and [{Cu2(L111)2}2(thiomorph)4] · 3thiomorph each contain two 5-coordinate and two 6-coordinate centres. Each of [Cu2(L444)2(THF)2] · 2THF and Cu2(L444)2(mpip)2] · H2O incorporate only 5-coordinate metal centres, with the latter complex forming a one-dimensional hydrogen bonded ribbon-like structure directed along the crystallographic a-axis. In keeping with the documented tendency for the smallest, least strained assembly to form in supramolecular self-assembly processes, the incorporation of the flexible {"}oxy{"} linkage between the 4,4'-linked phenylene rings of H2L333 results in generation of a dinuclear [Cu2L22] species rather than a trinuclear (triangular) [Cu3L333] species of the type formed by the more rigid bis-beta-diketonato ligand analogue in which the biphenylene rings separating the β-diketone domains are directly coupled in their 4,4' positions.",

keywords = "SUPRAMOLECULAR CHEMISTRY, BIS(BETA-DIKETONATE) LIGANDS, MACROCYCLIC COMPLEXES, H-1-NMR SPECTROSCOPY, DIKETONATO LIGANDS, SOLVENT-EXTRACTION, CRYSTAL-STRUCTURES, BUILDING-BLOCKS, BETA-DIKETONES, ION CHEMISTRY",

author = "Clegg, {Jack K.} and Feng Li and Jolliffe, {Katrina A.} and Lindoy, {Leonard F.} and Meehan, {George V.} and Simon Parsons and Tasker, {Peter A.} and White, {Fraser J.}",

year = "2013",

month = oct,

day = "21",

doi = "10.1039/c3dt51531a",

language = "English",

volume = "42",

pages = "14315--14323",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "39",

}

TY - JOUR

T1 - Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

AU - Clegg, Jack K.

AU - Li, Feng

AU - Jolliffe, Katrina A.

AU - Lindoy, Leonard F.

AU - Meehan, George V.

AU - Parsons, Simon

AU - Tasker, Peter A.

AU - White, Fraser J.

PY - 2013/10/21

Y1 - 2013/10/21

N2 - The sequential interaction of preformed [Cu2(L111)2(THF)2] (where H2L111 is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu2(L444)2] · 2H2O (where H2L444 is 1,1-(4,4'-oxybiphenylene)-bis(4,4-dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N'-dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di- and tetranuclear assemblies were obtained and their X-ray structures determined. Dinuclear [Cu2(L111)2(mpip)2] · 2mpip incorporates two 5-coordinate, square pyramidal metal centres as does tetranuclear [{Cu2(L111)2}2(dmpip)2] · 2dmpip. In contrast, dinuclear [Cu2(L111)2(dmpip)4] · dmpip and [{Cu2(L111)2}2(thiomorph)4] · 3thiomorph each contain two 5-coordinate and two 6-coordinate centres. Each of [Cu2(L444)2(THF)2] · 2THF and Cu2(L444)2(mpip)2] · H2O incorporate only 5-coordinate metal centres, with the latter complex forming a one-dimensional hydrogen bonded ribbon-like structure directed along the crystallographic a-axis. In keeping with the documented tendency for the smallest, least strained assembly to form in supramolecular self-assembly processes, the incorporation of the flexible "oxy" linkage between the 4,4'-linked phenylene rings of H2L333 results in generation of a dinuclear [Cu2L22] species rather than a trinuclear (triangular) [Cu3L333] species of the type formed by the more rigid bis-beta-diketonato ligand analogue in which the biphenylene rings separating the β-diketone domains are directly coupled in their 4,4' positions.

AB - The sequential interaction of preformed [Cu2(L111)2(THF)2] (where H2L111 is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu2(L444)2] · 2H2O (where H2L444 is 1,1-(4,4'-oxybiphenylene)-bis(4,4-dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N'-dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di- and tetranuclear assemblies were obtained and their X-ray structures determined. Dinuclear [Cu2(L111)2(mpip)2] · 2mpip incorporates two 5-coordinate, square pyramidal metal centres as does tetranuclear [{Cu2(L111)2}2(dmpip)2] · 2dmpip. In contrast, dinuclear [Cu2(L111)2(dmpip)4] · dmpip and [{Cu2(L111)2}2(thiomorph)4] · 3thiomorph each contain two 5-coordinate and two 6-coordinate centres. Each of [Cu2(L444)2(THF)2] · 2THF and Cu2(L444)2(mpip)2] · H2O incorporate only 5-coordinate metal centres, with the latter complex forming a one-dimensional hydrogen bonded ribbon-like structure directed along the crystallographic a-axis. In keeping with the documented tendency for the smallest, least strained assembly to form in supramolecular self-assembly processes, the incorporation of the flexible "oxy" linkage between the 4,4'-linked phenylene rings of H2L333 results in generation of a dinuclear [Cu2L22] species rather than a trinuclear (triangular) [Cu3L333] species of the type formed by the more rigid bis-beta-diketonato ligand analogue in which the biphenylene rings separating the β-diketone domains are directly coupled in their 4,4' positions.

KW - SUPRAMOLECULAR CHEMISTRY

KW - BIS(BETA-DIKETONATE) LIGANDS

KW - MACROCYCLIC COMPLEXES

KW - H-1-NMR SPECTROSCOPY

KW - DIKETONATO LIGANDS

KW - SOLVENT-EXTRACTION

KW - CRYSTAL-STRUCTURES

KW - BUILDING-BLOCKS

KW - BETA-DIKETONES

KW - ION CHEMISTRY

U2 - 10.1039/c3dt51531a

DO - 10.1039/c3dt51531a

M3 - Article

SN - 1477-9226

VL - 42

SP - 14315

EP - 14323

JO - Dalton Transactions

JF - Dalton Transactions

IS - 39

ER -

Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

Abstract

Keywords / Materials (for Non-textual outputs)

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Pressure Sensitive Complexformation based on self assembling ligands

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