Future molecular microelectronics require the electronic conductivity of the device to be tunable without impairing the voltage control of the molecular electronic properties. This work reports the influence of an interface between a semiconducting polyaniline polymer or a polar poly-D-lysine molecular film and one of two valence tautomeric complexes, i.e. , [Co III (SQ)(Cat)(4-CN-py) 2 ] ↔ [Co II (SQ) 2 (4-CN-py) 2 ] and [Co III (SQ)(Cat)(3-tpp) 2 ] ↔ [Co II (SQ) 2 (3-tpp) 2 ]. The electronic transitions and orbitals are identified using X-ray photoemission, X-ray absorption, inverse photoemission, and optical absorption spectroscopy measurements that are guided by density functional theory. Except for slightly modified binding energies and shifted orbital levels, the choice of the underlying substrate layer has little effect on the electronic structure. A prominent unoccupied ligand-to-metal charge transfer state exists in [Co III (SQ)(Cat)(3-tpp) 2 ] ↔ [Co II (SQ) 2 (3-tpp) 2 ] that is virtually insensitive to the interface between the polymer and tautomeric complexes in the Co II high-spin state.
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Exploring the molecular electronic device applications of synthetically versatile silicon pincer complexes as charge transport and electroluminescent layers
Hexacoordinate silicon pincer complexes using 2,6-bis(benzimidazol-2-yl)pyridine (bzimpy) ligands have been developed as a multifunctional, molecular electronic materials platform. We report the synthesis, characterization, and device application of a variety of Si(pincer) 2 complexes that exhibit tunable optoelectronic properties and excellent thermal stabilities. Promising, ambipolar charge carrier properties and excimeric electroluminescence were obtained from thermally deposited films using several device architectures. Incorporation of the complexes as a thin, interfacial contact and electron transport layer improved organic solar cell efficiencies by as much as 50%. The versatility and tailorability of this class of silicon complexes provides promising evidence for their future application in molecular electronic devices.
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- Award ID(s):
- 1800331
- NSF-PAR ID:
- 10347345
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 3
- Issue:
- 5
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 2373 to 2379
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract New emerging low‐dimensional such as 0D, 1D, and 2D nanomaterials have attracted tremendous research interests in various fields of state‐of‐the‐art electronics, optoelectronics, and photonic applications due to their unique structural features and associated electronic, mechanical, and optical properties as well as high‐throughput fabrication for large‐area and low‐cost production and integration. Particularly, photodetectors which transform light to electrical signals are one of the key components in modern optical communication and developed imaging technologies for whole application spectrum in the daily lives, including X‐rays and ultraviolet biomedical imaging, visible light camera, and infrared night vision and spectroscopy. Today, diverse photodetector technologies are growing in terms of functionality and performance beyond the conventional silicon semiconductor, and low‐dimensional nanomaterials have been demonstrated as promising potential platforms. In this review, the current states of progress on the development of these nanomaterials and their applications in the field of photodetectors are summarized. From the elemental combination for material design and lattice structure to the essential investigations of hybrid device architectures, various devices and recent developments including wearable photodetectors and neuromorphic applications are fully introduced. Finally, the future perspectives and challenges of the low‐dimensional nanomaterials based photodetectors are also discussed.
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Abstract The description of π‐donor amido moieties as ‘weak‐field’ ligands can belie the influence of metal‐ligand covalency on the overall ligand field of coordination complexes, which can in turn influence properties including the magnetic ground state and those of their excited states. In this contribution, the ligand fields of pseudo‐octahedral Ni(II) complexes supported by diarylamido pincer‐type amido ligands – three previously reported examples supported by asymmetric (2‐R‐phenanthridin‐4‐yl)(8‐quinolinyl)amido ligands (R = Cl, CF3,
t Bu;R L1 ) along with a new congener bearing a symmetricbis (8‐quinolinyl)amido ligand (BQA;L2 ) – were investigated in two ways. First, high‐frequency and ‐field electron paramagnetic resonance spectroscopy (HFEPR), SQUID magnetometry, and electronic absorption spectroscopy were used to determine the ligand field parameters. Second, the ability to electrochemically address ligand‐based oxidations despite metal‐centered SOMOs in the parentS =1 paramagnets was investigated, supported by time‐dependent density functional theory (TDDFT) identification of strong intervalence charge‐transfer (IVCT) transitions attributed to electronic communication between two Namidomoieties mediated by a Ni(II) bridge. These findings are discussed in the broader context of 3d transition metal coordination complexes of weak‐field π‐donor ligands. -
We systematically investigated iodine–metal and iodine–iodine bonding in van Koten’s pincer complex and 19 modifications changing substituents and/or the transition metal with a PBE0–D3(BJ)/aug–cc–pVTZ/PP(M,I) model chemistry. As a novel tool for the quantitative assessment of the iodine–metal and iodine–iodine bond strength in these complexes we used the local mode analysis, originally introduced by Konkoli and Cremer, complemented with NBO and Bader’s QTAIM analyses. Our study reveals the major electronic effects in the catalytic activity of the M–I–I non-classical three-center bond of the pincer complex, which is involved in the oxidative addition of molecular iodine I2 to the metal center. According to our investigations the charge transfer from the metal to the σ* antibonding orbital of the I–I bond changes the 3c–4e character of the M–I–I three-center bond, which leads to weakening of the iodine I–I bond and strengthening of the metal–iodine M–I bond, facilitating in this way the oxidative addition of I2 to the metal. The charge transfer can be systematically modified by substitution at different places of the pincer complex and by different transition metals, changing the strength of both the M–I and the I2 bonds. We also modeled for the original pincer complex how solvents with different polarity influence the 3c–4e character of the M–I–I bond. Our results provide new guidelines for the design of pincer complexes with specific iodine–metal bond strengths and introduce the local vibrational mode analysis as an efficient tool to assess the bond strength in complexes.more » « less
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Abstract Carbon doped two-dimensional (2D) hexagonal boron nitride nanosheets (BNNSs) are obtained through a CO 2 —pulsed laser deposition (CO 2 —PLD) technique on silicon dioxide (SiO 2 ) or molybdenum (Mo) substrates, showing - stable hysteresis characteristics over a wide range of temperatures, which makes them a promising candidate for materials based on non-volatile memory devices. This innovative material with electronic properties of n-type characterized in the form of back-to-back Schottky diodes appears to have special features that can enhance the device performance and data retention due to its functional properties, thermal-mechanical stability, and its relation with resistive switching phenomena. It can also be used to eliminate sneak current in resistive random-access memory devices in a crossbar array. In this sense constitutes a good alternative to design two series of resistance-switching Schottky barrier models in the gold/BNNS/gold and gold/BNNS/molybdenum structures; thus, symmetrical and non-symmetrical characteristics are shown at low and high bias voltages as indicated by the electrical current-voltage (I–V) curves. On the one hand, the charge recombination caused by thermionic emission does not significantly change the rectification characteristics of the diode, only its hysteresis properties change due to the increase in external voltage in the Schottky junctions. The addition of carbon to BNNSs creates boron vacancies that exhibit partially ionic character, which also helps to enhance its electrical properties at the metal-BNNS-metal interface.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1MA00737H
