Ruthenium Complexes with Protic Ligands: Influence of the Position of OH Groups and π Expansion on Luminescence and Photocytotoxicity.
Ruthenium Complexes with Protic Ligands: Influence of the Position of OH Groups and π Expansion on Luminescence and Photocytotoxicity.
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DOI：
10.3390/ijms24065980
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发表时间：
2023-03-22
影响因子：
5.6
通讯作者：
Papish, Elizabeth T. T.
中科院分区：
文献类型：
--
作者：
Oladipupo, Olaitan E. E.;Prescott, Meredith C. C.;Blevins, Emily R. R.;Gray, Jessica L. L.;Cameron, Colin G. G.;Qu, Fengrui;Ward, Nicholas A. A.;Pierce, Abigail L. L.;Collinson, Elizabeth R. R.;Hall, James Fletcher;Park, Seungjo;Kim, Yonghyun;McFarland, Sherri A. A.;Fedin, Igor;Papish, Elizabeth T. T.
采用二羟基联吡啶（dhbp）配体与旁观配体（N,N = bpy, phen, dop, Bphen）结合，研究了质子钌配合物对癌细胞的潜在活性及其光物理发光特性。这些配合物在π扩张的程度和近端（6,6 ' -dhbp）或远端（4,4 ' -dhbp）羟基的使用上各不相同。本文研究了8种配合物的酸性（含OH）形式、[(N，N)2Ru(N,N ' -dhbp)]Cl2形式和双去质子化（含O）形式。因此，这两种质子化态的存在给出了16种已被分离和研究的配合物。配合物7A [(dop)2Ru(4,4 ' -dhbp)]Cl2最近被合成并通过光谱和x射线晶体学进行了表征。本文还首次报道了三种配合物的去质子化形式。所研究的其他配合物已经在以前合成过。三种配合物是光激活的，表现出光细胞毒性。对数（Do/w）值的配合物被用来关联光细胞毒性与改善细胞摄取。对于含有6,6 ' -dhbp配体的Ru配合物1-4，光致发光研究（均在脱氧乙腈中进行）表明，空间应变导致光解离，这往往会降低质子化状态下的光致发光寿命和量子产率。对于含有4,4 ' -dhbp配体的Ru配合物5-8，去质子化的Ru配合物（5B-8B）具有较低的光致发光寿命和量子产率，这是由于猝灭引起的，猝灭涉及3LLCT激发态和电荷从[O2-bpy]2 -配体转移到N，N旁观配体。含有4,4′-dhbp钌的质子化羟基配合物（5A-8A）具有较长的发光寿命，其发光寿命随着N，N旁观配体上π膨胀的增加而增加。Bphen配合物8A的寿命最长，为3.45 μs，光致发光量子产率为18.7%。该络合物也表现出该系列中最好的光细胞毒性。较长的发光寿命与较高的单重态氧量子产率相关，因为三重态激发态的寿命可能足够长，可以与3O2相互作用产生1O2。
Protic ruthenium complexes using the dihydroxybipyridine (dhbp) ligand combined with a spectator ligand (N,N = bpy, phen, dop, Bphen) have been studied for their potential activity vs. cancer cells and their photophysical luminescent properties. These complexes vary in the extent of π expansion and the use of proximal (6,6′-dhbp) or distal (4,4′-dhbp) hydroxy groups. Eight complexes are studied herein as the acidic (OH bearing) form, [(N,N)2Ru(n,n′-dhbp)]Cl2, or as the doubly deprotonated (O− bearing) form. Thus, the presence of these two protonation states gives 16 complexes that have been isolated and studied. Complex 7A, [(dop)2Ru(4,4′-dhbp)]Cl2, has been recently synthesized and characterized spectroscopically and by X-ray crystallography. The deprotonated forms of three complexes are also reported herein for the first time. The other complexes studied have been synthesized previously. Three complexes are light-activated and exhibit photocytotoxicity. The log(Do/w) values of the complexes are used herein to correlate photocytotoxicity with improved cellular uptake. For Ru complexes 1–4 bearing the 6,6′-dhbp ligand, photoluminescence studies (all in deaerated acetonitrile) have revealed that steric strain leads to photodissociation which tends to reduce photoluminescent lifetimes and quantum yields in both protonation states. For Ru complexes 5–8 bearing the 4,4′-dhbp ligand, the deprotonated Ru complexes (5B–8B) have low photoluminescent lifetimes and quantum yields due to quenching that is proposed to involve the 3LLCT excited state and charge transfer from the [O2-bpy]2− ligand to the N,N spectator ligand. The protonated OH bearing 4,4′-dhbp Ru complexes (5A–8A) have long luminescence lifetimes which increase with increasing π expansion on the N,N spectator ligand. The Bphen complex, 8A, has the longest lifetime of the series at 3.45 μs and a photoluminescence quantum yield of 18.7%. This Ru complex also exhibits the best photocytotoxicity of the series. A long luminescence lifetime is correlated with greater singlet oxygen quantum yields because the triplet excited state is presumably long-lived enough to interact with 3O2 to yield 1O2.
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影响因子：
8.4
作者：
Lanquist AP;Gupta S;Al-Afyouni KF;Al-Afyouni M;Kodanko JJ;Turro C
通讯作者：
Turro C
影响因子：
4.3
作者：
Loftus, Lauren M.;Al-Afyouni, Kathlyn F.;Turro, Claudia
通讯作者：
Turro, Claudia
影响因子：
4.6
作者：
Hidayatullah, Achmad N.;Wachter, Erin;Glazer, Edith C.
通讯作者：
Glazer, Edith C.
多吡啶基型配体的生物学活性：对生物无机化学和光激活金属络合物的影响。
影响因子：
7.8
作者：
Hachey AC;Havrylyuk D;Glazer EC
通讯作者：
Glazer EC
影响因子：
15
作者：
Abrahamsson, Maria;Jager, Michael;Hammarstrom, Leif
通讯作者：
Hammarstrom, Leif