Synthesis, structure and properties of [Zn(dpa)(N3) 2] and [Zn(dpa)(N3)(NO3)]2 (dpa=2,2′-dipyridylamine): Composition tailored architectures

Doyel Bose; Sk Hafijur Rahaman; Golam Mostafa; Rosa D.Bailey Walsh; Michael J. Zaworotko; Barindra K. Ghosh

doi:10.1016/j.poly.2003.10.012

Synthesis, structure and properties of [Zn(dpa)(N₃) ₂] and [Zn(dpa)(N₃)(NO₃)]₂ (dpa=2,2′-dipyridylamine): Composition tailored architectures

Doyel Bose, Sk Hafijur Rahaman, Golam Mostafa, Rosa D.Bailey Walsh, Michael J. Zaworotko, Barindra K. Ghosh

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

Abstract

The synthetic details, characterization data and single crystal X-ray structural analyses of [Zn(dpa)(N₃)₂] (1) and [Zn(dpa)(N₃)(NO₃)]₂ (2) (dpa=2,2′- dipyridylamine) are described. Structural study reveals that the zinc(II) centre in 1 is in a pseudotetrahedral ZnN₄ environment ligated by two terminal azide N atoms and two pyridine N atoms of the chelator. The coordination polyhedron around each metal ion in dinuclear 2 is best described as a ZnN₄O₂ distorted octahedron linked by two end-on azido bridges. The mononuclear units in 1 are engaged in bifurcated intermolecular hydrogen bonding (N-H...N) between amine N of dpa and coordinated N of azide along with aromatic π-π stacking leading to a 2D sheet. In 2, the dinuclear units participate in intermolecular N-H...O hydrogen bonding between amine N of dpa and bound O of bidentate nitrate in combination with π-π interactions resulting to a 3D supramolecular continuum. 1 and 2 display high energy intraligand ¹(π-π*) fluorescence and intraligand ³(π-π*) phosphorescence in glassy solutions (DMF at 77 K). A band (372 nm) observed for both 1 and 2 in their solid-state emission spectra is an excimeric emission arising due to aromatic π-π interaction. The role of dpa, a tailored diimine (-N=C-NH-C=N-) in 1 and 2 is discussed towards functionalisation on crystal engineering and luminescence behaviour.

Original language	English
Pages (from-to)	545-552
Number of pages	8
Journal	Polyhedron
Volume	23
Issue number	4
DOIs	https://doi.org/10.1016/j.poly.2003.10.012
Publication status	Published - 12 Feb 2004
Externally published	Yes

Keywords

2,2′-Dipyridylamine
Crystal engineering
Dinuclear
Luminescence
Mononuclear
Zinc(II)azide

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10.1016/j.poly.2003.10.012

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@article{c54304a3100f49c08dc8e82f315312ae,

title = "Synthesis, structure and properties of [Zn(dpa)(N3) 2] and [Zn(dpa)(N3)(NO3)]2 (dpa=2,2′-dipyridylamine): Composition tailored architectures",

abstract = "The synthetic details, characterization data and single crystal X-ray structural analyses of [Zn(dpa)(N3)2] (1) and [Zn(dpa)(N3)(NO3)]2 (2) (dpa=2,2′- dipyridylamine) are described. Structural study reveals that the zinc(II) centre in 1 is in a pseudotetrahedral ZnN4 environment ligated by two terminal azide N atoms and two pyridine N atoms of the chelator. The coordination polyhedron around each metal ion in dinuclear 2 is best described as a ZnN4O2 distorted octahedron linked by two end-on azido bridges. The mononuclear units in 1 are engaged in bifurcated intermolecular hydrogen bonding (N-H...N) between amine N of dpa and coordinated N of azide along with aromatic π-π stacking leading to a 2D sheet. In 2, the dinuclear units participate in intermolecular N-H...O hydrogen bonding between amine N of dpa and bound O of bidentate nitrate in combination with π-π interactions resulting to a 3D supramolecular continuum. 1 and 2 display high energy intraligand 1(π-π*) fluorescence and intraligand 3(π-π*) phosphorescence in glassy solutions (DMF at 77 K). A band (372 nm) observed for both 1 and 2 in their solid-state emission spectra is an excimeric emission arising due to aromatic π-π interaction. The role of dpa, a tailored diimine (-N=C-NH-C=N-) in 1 and 2 is discussed towards functionalisation on crystal engineering and luminescence behaviour.",

keywords = "2,2′-Dipyridylamine, Crystal engineering, Dinuclear, Luminescence, Mononuclear, Zinc(II)azide",

author = "Doyel Bose and Rahaman, {Sk Hafijur} and Golam Mostafa and Walsh, {Rosa D.Bailey} and Zaworotko, {Michael J.} and Ghosh, {Barindra K.}",

year = "2004",

month = feb,

day = "12",

doi = "10.1016/j.poly.2003.10.012",

language = "English",

volume = "23",

pages = "545--552",

journal = "Polyhedron",

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TY - JOUR

T1 - Synthesis, structure and properties of [Zn(dpa)(N3) 2] and [Zn(dpa)(N3)(NO3)]2 (dpa=2,2′-dipyridylamine)

T2 - Composition tailored architectures

AU - Bose, Doyel

AU - Rahaman, Sk Hafijur

AU - Mostafa, Golam

AU - Walsh, Rosa D.Bailey

AU - Zaworotko, Michael J.

AU - Ghosh, Barindra K.

PY - 2004/2/12

Y1 - 2004/2/12

N2 - The synthetic details, characterization data and single crystal X-ray structural analyses of [Zn(dpa)(N3)2] (1) and [Zn(dpa)(N3)(NO3)]2 (2) (dpa=2,2′- dipyridylamine) are described. Structural study reveals that the zinc(II) centre in 1 is in a pseudotetrahedral ZnN4 environment ligated by two terminal azide N atoms and two pyridine N atoms of the chelator. The coordination polyhedron around each metal ion in dinuclear 2 is best described as a ZnN4O2 distorted octahedron linked by two end-on azido bridges. The mononuclear units in 1 are engaged in bifurcated intermolecular hydrogen bonding (N-H...N) between amine N of dpa and coordinated N of azide along with aromatic π-π stacking leading to a 2D sheet. In 2, the dinuclear units participate in intermolecular N-H...O hydrogen bonding between amine N of dpa and bound O of bidentate nitrate in combination with π-π interactions resulting to a 3D supramolecular continuum. 1 and 2 display high energy intraligand 1(π-π*) fluorescence and intraligand 3(π-π*) phosphorescence in glassy solutions (DMF at 77 K). A band (372 nm) observed for both 1 and 2 in their solid-state emission spectra is an excimeric emission arising due to aromatic π-π interaction. The role of dpa, a tailored diimine (-N=C-NH-C=N-) in 1 and 2 is discussed towards functionalisation on crystal engineering and luminescence behaviour.

AB - The synthetic details, characterization data and single crystal X-ray structural analyses of [Zn(dpa)(N3)2] (1) and [Zn(dpa)(N3)(NO3)]2 (2) (dpa=2,2′- dipyridylamine) are described. Structural study reveals that the zinc(II) centre in 1 is in a pseudotetrahedral ZnN4 environment ligated by two terminal azide N atoms and two pyridine N atoms of the chelator. The coordination polyhedron around each metal ion in dinuclear 2 is best described as a ZnN4O2 distorted octahedron linked by two end-on azido bridges. The mononuclear units in 1 are engaged in bifurcated intermolecular hydrogen bonding (N-H...N) between amine N of dpa and coordinated N of azide along with aromatic π-π stacking leading to a 2D sheet. In 2, the dinuclear units participate in intermolecular N-H...O hydrogen bonding between amine N of dpa and bound O of bidentate nitrate in combination with π-π interactions resulting to a 3D supramolecular continuum. 1 and 2 display high energy intraligand 1(π-π*) fluorescence and intraligand 3(π-π*) phosphorescence in glassy solutions (DMF at 77 K). A band (372 nm) observed for both 1 and 2 in their solid-state emission spectra is an excimeric emission arising due to aromatic π-π interaction. The role of dpa, a tailored diimine (-N=C-NH-C=N-) in 1 and 2 is discussed towards functionalisation on crystal engineering and luminescence behaviour.

KW - 2,2′-Dipyridylamine

KW - Crystal engineering

KW - Dinuclear

KW - Luminescence

KW - Mononuclear

KW - Zinc(II)azide

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U2 - 10.1016/j.poly.2003.10.012

DO - 10.1016/j.poly.2003.10.012

M3 - Article

AN - SCOPUS:1042301083

SN - 0277-5387

VL - 23

SP - 545

EP - 552

JO - Polyhedron

JF - Polyhedron

IS - 4

ER -

Synthesis, structure and properties of [Zn(dpa)(N₃) ₂] and [Zn(dpa)(N₃)(NO₃)]₂ (dpa=2,2′-dipyridylamine): Composition tailored architectures

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