Malaysian Journal of Analytical Sciences Vol 24 No 1 (2020): 11 - 20

 

 

 

 

Synthesis and SOLID-STATE structurAL ELUCIDATION of rhenium(I) complex with 1-cinnamoyl-3-(pyridIN-2-YL)pyrazole

 

(Sintesis dan Penentuan Struktur Pepejal Kompleks Renium(I) dengan 1-Sinamoil-3-(Piridin-2-il)Pirazola)

 

Wun Fui Mark-Lee¹, Yan Yi Chong², Azizul Hakim Lahuri¹, Mohammad B. Kassim²*

 

¹Department of Basic Science and Engineering, Faculty of Agriculture and Food Sciences,

Universiti Putra Malaysia Bintulu, 97008 Sarawak, Malaysia

²Centre for Advanced Materials and Renewable Resources, Faculty of Science and Technology,

Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

 

*Corresponding author:  mb_kassim@ukm.edu.my

 

 

Received: 20 November 2019; Accepted: 15 January 2020

 

 

Abstract

Re(I) complexes have been described as a promising tool for DNA probes. Rhenium(I) tricarbonyl complexes have favourable structural features suitable for DNA intercalation such as the new rhenium(I) tricarbonyl complex with polypyridyl ancillary ligand, namely, fac-[Re(CnPyPz)(CO)₃Cl] (CnPyPz = 1-cinnamoyl-3-(pyridin-2-yl)pyrazole). The complex was synthesised from the reaction of 1-cinnamoyl-3-(pyridin-2-yl)pyrazole and rhenium(I) pentacarbonyl chloride in toluene at refluxing temperature and characterised by infrared (IR), ultraviolet-visible (UV-Vis), ¹³C and ¹H NMR spectroscopies and X-ray crystallography. The IR spectrum featured the three n(CºO) signal for the rhenium moiety at 1862-2019 cm^-1 and other signals for the ligand namely n(C=O), n(C=N) and n(C=C) at 1724, 1609 and 1497 cm^-1, respectively. The ¹³C NMR spectra showed three CºO (190.0 – 198.1 ppm) signals whereas the ¹H spectrum for Re(CO)₃(CnPyPz)Cl exhibited two pairs of doublets (7.81 and 8.18 ppm) for the vinylic H of the cinnamoyl group. The complex exhibited a broad band corresponding to the metal-to-ligand charge transfer (MLCT) in the region of 360-390 nm. The Re(CO)₃(CnPyPz)Cl complex underwent a ligand exchange during the crystallisation process, involving one of the tricarbonyl groups with a chlorine atom to form the Re(CO)₂(CnPyPz)Cl₂ complex. The corresponding, Re(CO)₂(CnPyPz)Cl₂ crystal adopts a triclinic crystal system with a P-1 space group. The implementation of flexible CnPyPz ligand contributes to a dynamic supramolecular arrangement that facilitates both a planar π-π stacking arrangement accompanied with an appreciable globularity character via C−H···π and C≡O···π interconnections.

 

Keywords:  rhenium, carbonyl, π stacking, Hirshfeld, DNA probes

 

Abstrak

Kompleks Re(I) telah dikenali sebagai bahan yang berpotensi untuk prob DNA. Kompleks trikarbonil Re(I) mempunyai ciri struktur yang sesuai untuk interkalasi DNA seperti mana kompleks renium(I) trikarbonil dengan ligan ansilari polipiridina, fac-[Re(CnPyPz)(CO)₃Cl] (CnPyPz = 1-sinamoil-3-(piridin-2-il)pirazola). Kompleks ini telah disintesis daripada tindak balas 1-sinamoil-3-(piridin-2-il)pirazola dengan pentakarbonilklororenium(I) dalam toluena pada suhu refluks dan telah dicirikan dengan menggunakan spektroskopi inframerah (IR), ultralembahyung-cahaya nampak (UV-Vis), resonans magnet nukleus (NMR) ¹³C dan ¹H dan kristalografi sinar-X. Spektrum IR menunjukkan tiga jalur n(CºO) untuk moieti logam renium pada 1862-2019 cm^-1, dan isyarat ligan seperti n(C=O), n(C=N) dan n(C=C) masing-masing pada 1724, 1609 dan 1497 cm^-1. Spektrum NMR ¹³C menunjukkan tiga isyarat CºO pada julat 190.0 – 198.1 ppm manakala spektrum ¹H kompleks Re(CO)₃(CnPyPz)Cl menunjukkan proton vinil (CH=CH) kumpulan sinamoil sebagai dua pasangan dublet pada 7.81 dan 8.18 ppm. Kompleks Re(I) ini mempamerkan jalur yang lebar bagi pertukaran cas logam kepada ligan (MLCT) pada julat 360-390 nm. Kompleks Re(CO)₃(CnPyPz)Cl mengalami pertukaran ligan yang melibatkan pengoksidaan pusat logam Re(I) kepada Re(II) semasa proses penghabluran yang melibatkan salah satu daripada kumpulan trikarbonil dengan satu atom klorin untuk membentuk kompleks Re(CO)₂(CnPyPz)Cl₂. Kompleks ini menghablur dalam sistem kristal triklinik dengan kumpulan ruang P-1. Penggunaan ligan CnPyPz yang fleksibel menyumbang kepada susunan supramolekul yang membawa kepada susunan π-π satah berserta dengan sifat globular yang ketara melalui ikatan C−H···π dan C≡O···π. 

 

Kata kunci:  renium, karbonil, susunan π, Hirshfeld, prob DNA

 

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