Linear-Chain Structures of Platinum(II) Diimine Complexes

Connick, William B.; Marsh, Richard E.; Schaefer, William P.; Gray, Harry B.

doi:10.1021/ic961232v

Cited by 333 publications

(257 citation statements)

References 37 publications

(70 reference statements)

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“…This value is typical for the linear-chain structure of Pt II complexes with PtÁÁÁPt interactions. 21 The stacking pattern for the red form of [Pt-(CN) 2 (dcbpy)] is essentially the same as that found for the red form of [Pt(CN) 2 (bpy)]. However, it is noteworthy that the network structure constructed by hydrogen bonding for [Pt(CN) 2 (dcbpy)] has large cavities in the crystal.…”

Section: Temperature Dependence Of the Emissionsupporting

confidence: 57%

Luminescent Platinum Complexes Having Sensing Functionalities

Kato¹

2007

Bulletin of the Chemical Society of Japan

205

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Square-planar platinum(II) complexes often exhibit intense color and luminescence when they are stacked via selfassembly or bridging by ligands. The origin of the color and luminescence are the metal-metal electronic interactions, and thus, remarkable changes in color (i.e., chromism) are expected by controlling the PtÁÁÁPt interactions. The molecular arrangement of the assembled complex systems is sensitive to environmental factors such as temperature, pressure, solvent, and vapor. This account focuses on the sensing functionalities of luminescent platinum(II) complexes with 2,2 0 -bipyridine or its derivatives toward their environment. Especially, luminescence changes that are induced by the vapor molecules will be examined from the viewpoint of chemical sensing. The vapochromic behavior and structural aspects of the mononuclear and dinuclear platinum(II) complexes are discussed.

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Section: Temperature Dependence Of the Emissionsupporting

confidence: 57%

Luminescent Platinum Complexes Having Sensing Functionalities

Kato¹

2007

Bulletin of the Chemical Society of Japan

205

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“…On the basis of our previous work (17)(18)(19)(20)(21) and other related studies (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16), the newly formed UV-vis bands of complexes 1 and 2 at longer wavelength are assigned as MMLCT transitions, as a result of the self-assembly of the complexes induced by the oligonucleotides through metal⅐⅐⅐metal and ⅐⅐⅐ interactions. The newly formed emission bands are attributed to MMLCT triplet emission.…”

Section: Resultsmentioning

confidence: 83%

“…With a fixed molar ratio of complex 1 to nucleic acid base of 1:3, for poly(dT) 5 , which contains only five monomer nucleotide units, UV-vis and emission studies show only very small intensity changes, indicating that the self-assembly is quite weak. For poly(dT) 10 , UV-vis and emission studies indicate significant complex selfassembly, whereas for poly(dT) 15 , the spectroscopic changes are comparable to those with poly(dT) 25 , indicating strong complex helical self-assembly. We also tested poly(dT) 20 and poly(dT) 50 , and both give results similar to poly(dT) 25 .…”

Section: Resultsmentioning

confidence: 93%

“…Depending on the extent of the metal⅐⅐⅐metal and the ligand ⅐⅐⅐ stacking interactions, different colors could be observed (3,4). Square planar platinum(II) complexes belong to a particularly interesting class of this type of complexes, as a result of their rich spectroscopic and luminescence properties revealed during the past few decades (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16).…”

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confidence: 99%

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Single-stranded nucleic acid-induced helical self-assembly of alkynylplatinum(II) terpyridyl complexes

Chan

Wong

et al. 2006

Proc. Natl. Acad. Sci. U.S.A.

172

124

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Single-stranded nucleic acids, which carry multiple negative charges in an aqueous medium at near neutral pH, are found to induce the aggregation and self-assembly of the positively charged alkynylplatinum(II) terpyridyl complexes via electrostatic binding of the platinum complexes to the single-stranded nucleic acids, as revealed by the appearance of new UV-vis absorption and emission bands upon addition of single-stranded nucleic acids to a buffer solution of the complex. Changes in the intensity and pattern of circular dichroism (CD) spectroscopy are also observed, many of which are consistent with the assembly of the platinum complexes into helical structures, via metal⅐⅐⅐metal and ⅐⅐⅐ stacking interactions. The induced spectroscopic property changes are found to depend on the structural properties of the nucleic acids.helicity ͉ noncovalent interactions ͉ platinum complex N ucleic acids are, in a sense, the most fundamental and important class of biomolecules in a living cell. Detection of nucleic acids, analysis of their sequence, structure, and the corresponding properties, as well as their self-replication, interactions with regulation factors, and the details of transcription and translation are among the major foci of numerous biochemical and biophysical research works (1, 2). Single-stranded nucleic acid sensing and characterization are therefore of great importance, which not only can help us to understand how the cell functions and to assist biological research, but also facilitate the development of new tools for disease diagnosis and treatment and new drug developments.It has been known for many years that many of the square planar metal complexes arrange themselves into highly ordered extended linear chain or oligomeric structures in the solid state. Depending on the extent of the metal⅐⅐⅐metal and the ligand ⅐⅐⅐ stacking interactions, different colors could be observed (3, 4). Square planar platinum(II) complexes belong to a particularly interesting class of this type of complexes, as a result of their rich spectroscopic and luminescence properties revealed during the past few decades (3-16).Recently, we have synthesized a number of platinum(II) polypyridyl alkynyl complexes that show interesting spectroscopic and luminescence properties (17-21). One particularly interesting observation is that solvents of different polarity and also polyacrylate could induce the aggregation of the positively charged platinum complexes in organic solvent mixtures (19, 21). As a result, remarkable spectroscopic property changes were observed. Because single-stranded nucleic acids carry multiple negatively charged phosphate functional groups, they are polyanions. It is therefore reasonable to envisage that single-stranded nucleic acids may have the possibility to induce the self-assembly of the square planar platinum(II) complexes in an aqueous environment. Here, we describe the synthesis and characterization of a water-soluble platinum(II) terpyridyl alkynyl complex, [Pt(tpy)C'CC'CCH 2 OH]OTf (1) (Fig. 1), and it...

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“…Detailed analysis of temperature-dependent UV-visible absorption spectra of the nanostructured tubular aggregates also provided insights into the assembly mechanism and showed the role of metal−metal interactions in the cooperative supramolecular polymerization of the amphiphilic platinum(II) complexes. noncovalent interactions | platinum complex | nanoaggregates S quare-planar d 8 platinum(II) polypyridine complexes have long been known to exhibit intriguing spectroscopic and luminescence properties (1-54) as well as interesting solid-state polymorphism associated with metal−metal and π−π stacking interactions (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)25). Earlier work by our group showed the first example, to our knowledge, of an alkynylplatinum(II) terpyridine system [Pt(tpy)(C ≡ CR)] + that incorporates σ-donating and solubilizing alkynyl ligands together with the formation of Pt···Pt interactions to exhibit notable color changes and luminescence enhancements on solvent composition change (25) and polyelectrolyte addition (26).…”

mentioning

confidence: 99%

Self-assembly of alkynylplatinum(II) terpyridine amphiphiles into nanostructures via steric control and metal–metal interactions

Leung

Wong

Yam

2016

Proc. Natl. Acad. Sci. U.S.A.

102

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A series of mono-and dinuclear alkynylplatinum(II) terpyridine complexes containing the hydrophilic oligo(para-phenylene ethynylene) with two 3,6,9-trioxadec-1-yloxy chains was designed and synthesized. The mononuclear alkynylplatinum(II) terpyridine complex was found to display a very strong tendency toward the formation of supramolecular structures. Interestingly, additional end-capping with another platinum(II) terpyridine moiety of various steric bulk at the terminal alkyne would lead to the formation of nanotubes or helical ribbons. These desirable nanostructures were found to be governed by the steric bulk on the platinum(II) terpyridine moieties, which modulates the directional metal−metal interactions and controls the formation of nanotubes or helical ribbons. Detailed analysis of temperature-dependent UV-visible absorption spectra of the nanostructured tubular aggregates also provided insights into the assembly mechanism and showed the role of metal−metal interactions in the cooperative supramolecular polymerization of the amphiphilic platinum(II) complexes. noncovalent interactions | platinum complex | nanoaggregates S quare-planar d 8 platinum(II) polypyridine complexes have long been known to exhibit intriguing spectroscopic and luminescence properties (1-54) as well as interesting solid-state polymorphism associated with metal−metal and π−π stacking interactions (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)25). Earlier work by our group showed the first example, to our knowledge, of an alkynylplatinum(II) terpyridine system [Pt(tpy)(C ≡ CR)] + that incorporates σ-donating and solubilizing alkynyl ligands together with the formation of Pt···Pt interactions to exhibit notable color changes and luminescence enhancements on solvent composition change (25) and polyelectrolyte addition (26). This approach has provided access to the alkynylplatinum(II) terpyridine and other related cyclometalated platinum(II) complexes, with functionalities that can self-assemble into metallogels (27-31), liquid crystals (32, 33), and other different molecular architectures, such as hairpin conformation (34), helices (35-38), nanostructures (39-45), and molecular tweezers (46, 47), as well as having a wide range of applications in molecular recognition (48-52), biomolecular labeling (48-52), and materials science (53, 54). Recently, metalcontaining amphiphiles have also emerged as a building block for supramolecular architectures (42)(43)(44)(55)(56)(57)(58)(59). Their self-assembly has always been found to yield different molecular architectures with unprecedented complexity through the multiple noncovalent interactions on the introduction of external stimuli (42)(43)(44)(55)(56)(57)(58)(59).Helical architecture is one of the most exciting self-assembled morphologies because of the uniqueness for the functional and topological properties (60-69). Helical ribbons composed of amphiphiles, such as diacetylenic lipids, glutamates, and peptidebased amphiphiles, are often precursors for the growth of tubular structures on an ...

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Linear-Chain Structures of Platinum(II) Diimine Complexes

Cited by 333 publications

References 37 publications

Luminescent Platinum Complexes Having Sensing Functionalities

Luminescent Platinum Complexes Having Sensing Functionalities

Single-stranded nucleic acid-induced helical self-assembly of alkynylplatinum(II) terpyridyl complexes

Self-assembly of alkynylplatinum(II) terpyridine amphiphiles into nanostructures via steric control and metal–metal interactions

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