1D Polymeric Platinum Cyanoximate: A Strategy toward Luminescence in the Near-Infrared Region beyond 1000 nm

Klaus, Danielle R.; Keene, Matthew; Silchenko, Svitlana; Berezin, Mikhail Y.; Gerasimchuk, Nikolay

doi:10.1021/ic502805h

Cited by 43 publications

(52 citation statements)

References 92 publications

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“…Recently we reported the chemistry and photoluminescence properties of the first mixed valence Pt-cyanoximate. 48 Two other complexes presented in this work widen the series of newly discovered NIR emitters that could be useful for biomedical research.…”

Section: Resultsmentioning

confidence: 95%

“…The green color is a combination of yellow (from n →π* transition in the anion) and blue color originated as the result of a charge-transfer band between the Pt centers and cyanoximes in a stack. 47, 48 Polar donor solvents tend to quickly discolor green solutions into yellow which indicates disaggregation of coordination polymers into yellow monomeric units Pt(MCO) 2 and Pt(PiPCO) 2 (ESI 48, 52, 53). Crystal structures of those have been determined (Figure 3 and discussion below).…”

Section: Resultsmentioning

confidence: 99%

“…The latter is assigned to be dσ* ➔ σ(π*) MMLCT. 90 Finally, based on the studies carried out, 48 the wavelength of 770 nm was selected as an excitation energy for recording the emission spectra of the solid 1D polymeric [Pt(MCO) 2 ] n and [Pt(PiPCO) 2 ] n which are presented below.…”

Section: Resultsmentioning

confidence: 99%

“…Such a technique is commonly used in FTIR measurements, 57 but was originally also proposed for the absorption spectra in the past. 48 Also, we prepared KBr pellets with 1%, 0.5% 0.1% by weight amounts of dark-green [Pt(MCO) 2 ] n and [Pt(PiPCO) 2 ] n complexes to investigate the effect of the concentration on the emission properties of polymers. Finally, we studied pure powdery samples of Pt-cyanoximate polymers to compare their emission with solid solutions in KBr pellets.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, our interest in mixed valence oximes-based coordination polymers of platinum is two-fold: 1) several Pt-cyanoximates have demonstrated significant in vitro cytotoxicity against human cancer cells at the level of cisplatin; 36, 38 2) we recently discovered that one of those new Pt complexes with N,N′-diethylamino-2-oximino-2-cyanoacetamide (DECO) 48 self-assemble in solutions into 1D, intensely colored mixed valence species that are semiconductors at ambient conditions in solid state. Therefore, these complexes can be viewed as suitable candidates for theranostic applications because they combine an imaging/diagnostic possibility and therapeutic potential as well.…”

Section: Introductionmentioning

confidence: 99%

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Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

et al. 2017

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Several complexes of “PtL2” composition containing two cyanoxime anions – 2-oximino-2-cyano-N-piperidineacetamide (PiPCO−) and 2-oximino-2-cyano-N-morpholylacetamide (MCO−) have been obtained and characterized both in solutions and in solid state. Complexes exist as two distinct polymorphs: monomeric yellow complexes, and dark-green [PtL2]n 1D polymers, while for the MCO− anion a red, solvent containing dimeric [Pt(MCO)2xDMSO]2 complex also has been isolated. The interconversion of polymorphs was investigated. The monomeric PtL2 units are arranged into the anisotropic extended solid [PtL2]n polymers with the help of Pt—Pt metallophilic interactions. Crystal structures of monomeric PtL2 (L= PiPCO−, MCO−) and red dimeric [Pt(MCO)2xDMSO]2 complexes were determined and revealed the cis-arrangement of cyanoxime anions. The Pt-Pt distance in the “head-to-tail” red dimer was found to be 3.133 Å. The structure of polymeric [Pt(PiPCO)2]n compound was elucidated using the EXAFS method and evidenced the formation of the Pt-wire with ~3.15 Å intermetallic separations. The EPR spectra of both 1D polymers at variable temperatures indicate the absence of Pt(III) species. Both pure dark-green [PtL2]n polymers showed considerable room temperature electrical conductivity of 20–30 S/cm, which evidences the formation of mixed valence Pt(II)/Pt(IV) system. We discovered that these 1D polymeric [PtL2]n complexes show an intense NIR fluorescence beyond 1000 nm, while yellow monomeric PtL2 complexes are not emissive at all. The room temperature excitation spectra of 1D polymeric [PtL2]n complexes demonstrated their strong emission beyond 1000 nm regardless of the used excitation wavelength between 350 and 800 nm, which is typical of systems with delocalized charge carriers. For the first time the formation of mixed valence “metal wire” assembled by metallophilic interactions is directly linked both with an intense fluorescence in the NIR region of spectrum and the electrical conductivity. The effect of concentration of [PtL2]n complexes dispersed in the dielectric salt matrix on the photoluminescence wavelength and intensity was investigated. Both polymers show a remarkably high for this region of spectrum quantum yield reaching ~2%. Variable temperature emission of polymeric [PtL2]n in the −190 - +60°C range was studied as well.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

et al. 2017

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Functional Pyrimidinyl Pyrazolate Pt(II) Complexes: Role of Nitrogen Atom in Tuning the Solid‐State Stacking and Photophysics

Ganesan

Hung

Tso

et al. 2019

Adv Funct Materials

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Pt(II) metal complexes are known to exhibit strong solid-state aggregation and are promising for realization of efficient emission in fabrication of organic light emitting diodes (OLED) with nondoped emitter layer. Four pyrimidine-pyrazolate based chelates, together with four isomeric Pt(II) metal complexes, namely: [Pt(pm2z) 2 ], [Pt(tpm2z) 2 ], [Pt(pm4z) 2 ], and [Pt(tpm4z) 2 ], are isolated and systematically investigated for their structure-property relationships for practical OLED applications. Detailed single molecular and aggregated structures are revealed by photophysical and mechanochromic measurements, grazing-incidence X-ray diffraction, and theoretical approaches. These results suggest that these Pt(II) emitters pack like a deck of playing cards under vacuum deposition, and their emission energy is not only affected by the single molecular designs, but notably influenced by their intermolecular packing interaction, i.e., Pt···Pt separations that are arranged in the order: [Pt(tpm4z) 2 ] > [Pt(pm4z) 2 ] > [Pt(tpm2z) 2 ] > [Pt(pm2z) 2 ]. Nondoped OLED with emission ranging from green to red are prepared, to which the best performances are recorded for [Pt(tpm2z) 2 ], giving maximum external quantum efficiency (EQE) of 27.5% at 10 3 cd m −2 , maximum luminance of 2.5 × 10 5 cd m −2 at 17 V, and with stable CIE x,y of (0.56, 0.44).computers, notepads, and cell phones. Their efficiencies have been improved during the past two decades using suitable third-row transition-metal phosphors as emitters. Among these emitters, Pt(II) metal complexes have been attracting intensive studies owing to their higher stability and intense luminescence at room temperature (RT). [1] However, in contrast to the Ir(III) emitters with d 6 -electronic configuration and octahedral coordination structure, [2] the Pt(II) emitters possesses distinctive d 8 -configuration and square planar geometry, which induced a greater tendency in forming π-π-stacking interaction between adjacent molecules in solid state. As for application, this aggregation is capable of tuning emission to lower energy region of the visible spectra and even further into the near-infrared (NIR), which allows versatile prospective in applications for this class of emitters.Many aggregated Pt(II) complexes have been synthesized, for which their structures can be differentiated into two classes. One is best represented by those bearing a linear Pt n architecture and with Pt···Pt distance of less than 3.4 Å; the latter is the sum of van del wall radii of

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Modulation of Solid‐State Aggregation of Square‐Planar Pt(II) Based Emitters: Enabling Highly Efficient Deep‐Red/Near Infrared Electroluminescence

Chen

Sukpattanacharoen

Chan

et al. 2020

Adv Funct Materials

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The design of square‐planar Pt(II) complexes with highly efficient solid‐state near infrared (NIR) luminescence for electroluminescence is attractive but challenging. This study presents the fine‐turning of excited‐state properties and application of a series of isoquinolinyl pyrazolate Pt(II) complexes that are modulated by steric demanding substituents. It reveals that the bulky substituents do not always disfavor metallophilic Pt···Pt interactions. Instead, π–π stacking among chelates, which are fine‐tuned by the associated substituents, also exerts strong influence to the metal‐metal‐to‐ligand charge transfer (MMLCT) transition character. Theoretical calculations indicate that Pt···Pt contacts become more relevant in the trimers rather than the dimers, especially in their T1 states, associated with a change from mixed 3LC/3MLCT transition in the monomer/dimer to mixed 3LC/3MMLCT transition character in the trimer. Electroluminescence devices affording intense deep‐red/NIR emission (near 670 nm) with unprecedentedly high external quantum efficiency over 30% are demonstrated. This work provides deep insights into formation MMLCT transition of square‐planar Pt(II) complexes and efficient molecular design for deep‐red/NIR electroluminescence.

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1D Polymeric Platinum Cyanoximate: A Strategy toward Luminescence in the Near-Infrared Region beyond 1000 nm

Cited by 43 publications

References 92 publications

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

Functional Pyrimidinyl Pyrazolate Pt(II) Complexes: Role of Nitrogen Atom in Tuning the Solid‐State Stacking and Photophysics

Modulation of Solid‐State Aggregation of Square‐Planar Pt(II) Based Emitters: Enabling Highly Efficient Deep‐Red/Near Infrared Electroluminescence

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