4730-54-5Relevant academic research and scientific papers
Phosphoric triamides. 31Phosphorus NMR chemical shift as a function of the P-N bond characteristics
Bourne, Susan A.,Mbianda, Xavier Y.,Modro, Tomasz A.,Nassimbeni, Luigi R.,Wan, Huijie
, p. 83 - 88 (1998)
Six phosphoric triamides in which amide nitrogens are incorporated into an increasing number (from 0 to 3) of the 1,3,2-diazaphospholidin-2-one rings have been prepared and their crystal structures have been determined. The structural changes from the non-cyclic to the mono-, di- and tri-cyclic systems result in the decrease of the N-P-N bond angles and the increase of the P-N bond distance. These changes are paralleled by a strong deshielding of the 31P nucleus, leading to an exceptionally high δp value for the tricyclic derivative. The δp-structural parameters relationship is discussed in terms of the changes in hybridization of phosphorus and the variation in the P-N bond order.
A high-nuclearity metal-cyanide cluster [Mo6Cu14] with photomagnetic properties
Bridonneau,Chamoreau,Gontard,Cantin,Von Bardeleben,Marvaud
, p. 9412 - 9418 (2016)
A high-nuclearity metal-cyanide cluster [Mo6Cu14] has been prepared and its photomagnetic properties investigated. The photoswitchable magnetic phenomenon observed is thermally reversible (T ≈ 230 K). In the field of photomagnetism, [Mo6Cu14] represents a unique example of a nanocage and the highest nuclearity observed so far.
Measurement of the rate of copper(II) exchange for 64Cu complexes of bifunctional chelators
Maheshwari, Vidhi,Dearling, Jason L.J.,Treves, S. Ted,Packard, Alan B.
, p. 318 - 323 (2012)
Measurement of the rate of loss of 64Cu from the chelators used in the preparation of 64Cu-labeled proteins is critical to the development of effective 64Cu-labeled radiopharmaceuticals. Typically, however, this assessment has been made indirectly, by comparison of the relative uptake of the labeled proteins in the liver, or under non-physiological conditions such as hot 5 M HCl. In the present study, we measured the rate of loss of 64Cu from a series of chelators (DOTA, TETA, and NOTA) that are commonly used to label proteins as a function of [Cu2+] (1, 2, and 5 μM) and pH (7.5, 6.0. and 5.0). We found that 64Cu-NOTA is somewhat more kinetically stable than 64Cu-TETA and that both 64Cu-NOTA and 64Cu-TETA are much more kinetically stable than 64Cu-DOTA. Furthermore, the rate of loss of 64Cu from Cu-DOTA increased with higher [Cu 2+] and pH while the rate of loss of 64Cu from Cu-TETA and Cu-NOTA was minimally dependent on [Cu2+] and pH. These results suggest that NOTA is preferable to TETA and DOTA for the preparation of 64Cu-labeled proteins.
DINUCLEATING LIGAND OR DINUCLEAR METAL COMPLEX
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Paragraph 0048; 0056-0057, (2021/03/19)
To provide a dinuclear metal complex that can be synthesized simply and easily and has a proper anticancer action.SOLUTION: The present disclosure provides a dinucleating ligand represented by the following formula (I) and a dinuclear metal complex thereof (where X is H or a substituted carbamoyl group, R1, R2, R3, and R4 independently represent H or a C1-8 linear or branched alkyl group).SELECTED DRAWING: None
Synthesis method of 1, 4, 7-triazacyclononane
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Paragraph 0010-0019, (2021/09/01)
The invention provides a synthesis method of 1, 4, 7-triazacyclononane. The preparation method comprises the step of: carrying out condensation ring-closure reaction on N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride and ethylenediamine at low temperature to obtain 1, 4, 7-triazacyclononane. According to the method, the reaction temperature ranges from -50 DEG C to -30 DEG C, and the molar ratio of N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride to ethylenediamine is 1: (0.95-1). 4-dimethylaminopyridine (DMAP) is adopted as an acid-binding agent, and the molar ratio of the DMAP to the N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride is (3.9-4.1): 1. Carbon tetrachloride is selected as a reaction solvent, and the mass ratio of the carbon tetrachloride to the N, N'-bis (2-chloroethyl) ethylenediamine hydrochloride is 2: 1. According to the process, other side reactions can be effectively avoided, the highest reaction yield can reach 78% or above, and the product purity can reach 94% or above.
Second-Sphere Interaction Promoted Turn-On Fluorescence for Selective Sensing of Organic Amines in a TbIII-based Macrocyclic Framework
Huang, Xianqiang,Liu, Qingzhi,Liu, Shixi,Ma, Shengqian,Nafady, Ayman,Niu, Zheng,Ren, Junyu,Tsai, Chen-Yen,Ye, Yingxiang
supporting information, p. 23705 - 23712 (2021/09/22)
Guided by a second-sphere interaction strategy, we fabricated a Tb(III)-based metal—organic framework (MMCF-4) for turn-on sensing of methyl amine with ultra-low detection limit and high turn-on efficiency. MMCF-4 features lanthanide nodes shielded in a nonacoordinate geometry along with secondary coordination spheres that are densely populated with H-bond interacting sites. Nonradiative routes were inhibited by binding-induced rigidification of the ligand on the second coordination sphere, resulting in luminescence amplification. Such remote interacting mechanism involved in the turn-on sensing event was confirmed by single-crystal X-ray diffraction and molecular dynamic simulation studies. The design of both primary and secondary coordination spheres of Tb(III) enabled the first turn-on sensing of organic amines in aqueous conditions. Our work suggests a promising strategy for high-performance turn-on sensing for Ln-MOFs and luminous materials driven by other metal chromophores.
An Efficient Synthesis of N,N,N-Substituted 1,4,7-Triazacyclononane
Huang, Yong,Liu, Yajing,Liu, Song,Wu, Renbo,Wu, Zehui
, p. 1546 - 1551 (2018/04/20)
A new and efficient synthetic approach is reported for various N,N,N-substituted 1,4,7-triazacyclononanes (TACN) in moderate to excellent yields, with optimization of the reaction sequences and conditions of the intermediate 1,4,7-tribenzyl-1,4,7-triazonane-2,6-dione reduction with LiAlH4, removal of benzyl with Pd/C, and alkylation reactions. This reaction scheme provides a convenient and flexible method to prepare various N,N,N-substituted TACN derivatives.
Synthesis methods of 1, 4, 7-triazacyclononane and derivatives thereof and obtained products
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, (2018/07/30)
The invention provides a synthesis method of 1, 4, 7-triazacyclononane. The synthesis method comprises the following steps: synthesizing an intermediate 1, 4, 7-tribenzyl-1, 4, 7-triazacyclononane-2,6-dione from N, N'-bis(N-benzyl-2-chloroacetamide) ethylenediamine and benzylamine as raw materials, and then reducing to remove benzyls to obtain the 1, 4, 7-triazacyclononane. The invention furthersynthesis methods of N, N', N'-1, 4, 7-triazacyclononane derivatives and corresponding products synthesized by the synthesis methods. The invention has the advantages as follows: the cost is low; theoperability is strong; N, N', N'-1, 4, 7-triazacyclononane derivatives with different substituents are selectively synthesized under a controllable reaction condition; the synthesis methods are applicable to industrial production and are applicable to synthesis of different types of triazacyclononane derivatives with different substituents; the implementation value and benefits are relatively high; the products have a potential application value in the field of radiopharmaceutical chemical multifunctional chelating agents, ion recognition, coordination chemistry and the like.
Comparative studies of the electronic, binding and photophysical properties of a new nona-dentate hemi-cage tripodal HQ pendant trizaza-macrocycle with unfilled, half-filled and completely filled lanthanide ions
Baral, Minati,Kanungo, B. K.,Rohini
, p. 16040 - 16059 (2018/10/04)
The present paper describes the comparative studies of the electronic, photophysical and binding properties of a new C3-symmetric polydentate ligand, 1,4,7-tris-{(5-methylene-8-hydroxyquinoline)-1,4,7-triazacyclononane} (9N3Me5Ox), and its complexes with 4f0, 4f7, and 4f14 metal ions (La3+, Gd3+, and Lu3+) by experimental and theoretical methods using DFT, TDDFT, TDDFTB, ETS-NOCV, NBO and Ligand Field DFT (LFDFT). The ligand and the complexes were synthesized and characterized through elemental analysis, molar conductance, TGA, FT-IR, FT-NMR, 1H-1H COSY and ESI-mass spectrometry techniques. The spectral data and structural studies revealed the formation of nine-coordinate compounds with the general formula [Ln(9N3Me5Ox)(H2O)3], in which the nonadentate chelator acted as a trinegative hexadentate ligand coordinating to the metal ions through three sets of O,N-donors of 8-hydroxyquinoline groups and three coordinated water molecules. The molecular modeling studies suggest that the metal ion can be easily encapsulated in its central cavity forming hemi-cage complexes without altering the basic metal-ligand coordination sphere. The nature of the bonding between the lanthanide ions and 9N3Me5Ox3?, elucidated by means of the natural bond orbital (NBO), Morokuma-Ziegler energy decomposition analysis (ETS-NOCV) scheme, suggests that the Ln-L bonds are more electrostatic (～82percent) than covalent (～18percent). The covalent character of the complexes increases in the order Lu > La > Gd. The photoluminescence spectral studies of the metal complexes revealed that the observed luminescence of the compounds in the solid state and solution is of different origin. The vibrational, 1H and 13C NMR spectral data obtained from the DFT optimized structures showed good agreement with the experimental results. The excitation and emission behaviours of the ligand and the complexes were established by molecular orbital analysis of the ground state DFT geometry as well as of the excited state optimized geometry using TD-DFT and TD-DFTB orbital analysis, excitation and emission properties.
Using iSUSTAIN to validate the chemical attributes of different approaches to the synthesis of tacn and bridged (bis)tacn ligands
Coghlan,Campi,Jackson,Hearn
supporting information, p. 5477 - 5484 (2016/10/21)
Using green chemistry principles, alternative approaches for the synthesis of commercially important aza-macrocyclic tacn and (bis)tacn derivatives have been investigated to determine the step average and overall efficiency of these synthetic methods. Based on analytical metrics derived from the iSUSTAIN toolkit, the Richman-Atkins route for the synthesis of tacn (1) was found to be the more efficient; however an alternate route was shown to be preferable for the synthesis of (bis)tacn (2) compounds. The outcome of this study documents the importance of rigorous analysis of synthetic procedures for such aza-macrocyclic compounds in terms of their green chemistry attributes, in order to delineate how alternative synthetic methods can be ranked, more innovative procedures selected to improve productivity and yield, and synthetic methods deployed to achieve greater levels of waste reduction, reduced use of hazardous chemicals and lower environmental impact.
