z Catalysis Functional Substituted Phthalocyanines Bearing Ter– pyridine Complexes as Macromolecular Oxidation Catalysts for Bleaching Systems Pinar Sen, [a] S. Zeki Yildiz,* [a] Necmi Dege, [b] Mehmet Atakay, [c] and Bekir Salih [c] The present study dealing with the oxidation catalysts using in laundry bleaching process comprises of the complexion of 4’- (N-2-phthalonitrile-N-methylamino)-2,2’:6’,2’’-terpyridine (2) with the related MnCl 2 .4H 2 O and CoCl 2 .6H 2 O salts in ethanol to obtain 4’-(N-2-phthalonitrile-N-methylamino)-2,2’:6’,2’’-terpyri- dine-Mn (II) complex (3) and 4’-(N-2-phthalonitrile-N-methyla- mino)-2,2’:6’,2’’-terpyridine-Co (II) complex (4). Terpyridine metal complexes substituted Zinc phthalocyanines, Tetrakis [4’-(N-2- phthalonitrile-N-methylamino)-2, 2’: 6’, 2’’-terpyridine-Mn(II) complex] phthalocyaninato zinc(II) (5) and Tetrakis [4’-(N-2- phthalonitrile-N-methylamino)-2,2’:6’,2’’-terpyridine-Co(II) com- plex] phthalocyaninato zinc(II) (6) were also prepared by the tetramerization of the terpyridine-metal complexes (3, 4) in the presence of ZnCl 2 . FT-IR, 1 H-NMR, 13 C-NMR, UV-Vis, ESI-MS and MALDI-MS spectra were applied to characterize the prepared compounds. 4-nitrophthalonitrile and some other starting materials crystallized in the synthetic pathway. 4-nitrophthalo- nitrile crystalizes in different morphology and 4’-(N-2- Hydrox- yehyl-N-methylamino)-2, 2’ : 6’, 2’’- terpyridine (1) crystallizes in the monoclinic, space group. The compound 2 and 3 crystallize in the monoclinic space group. The bleach performances of the prepared terpyridine complexes (3, 4) and their phthalocyanine derivatives (5, 6) were examined by the degradation of Morin dye by using online spectrophotometric method (OSM). Introduction 2,2’:6’,2’’-terpyridine has been widely studied since Morgan and Bustall first described the synthesis in 1932. [1] These studies based on complex formation as effective complexing agents, [2] were about photochemical properties [3] and building blocks in supramolecular science. [4] More recently, these compounds have also gained considerable attention for a wide range of applications such as photosensitizers for solar-energy conver- sion process, environmental sensors and DNA metallo intercala- tors. [5] There are also some examples for terpyridine ligands in the preparation of luminescent materials which have potentials for protein labeling applications. [6] 2,2’:6’,2’’-terpyridine generally acts as a tridentate N 3 donor and the complexes can be formed with various metals in different oxidation states. Recently, several studies have been published on the subject of functionalized terpyridines. [7] Especially, 4’-functionalized terpyridines were examined in the field of terpyridine complexes, ranging from mononuclear complexes to supramolecular architectures as versatile for building blocks. [8] Appended substituent groups have been utilized to tailor the properties of their complexes, as well. Phthalocyanines (Pcs) possessing 18 p-electrons have raised as promising building blocks for the construction of covalent conjugate and functional supramolecular molecular devices. Pcs exhibit architectural flexibility. A large variety of substitu- ents can be attached to the macrocycle core. In fact, in combination with other functional groups is a challenging topic at the center of molecular engineering. The construction of multicomponent systems including polypyridiyl ligands and phthalocyanines might be considered as complementary systems with excellent molecular architecture to have unique catalytic properties. The exceptional catalytic properties of phthalocyanines, such as oxidation of olefins, alkanes, alcohols and aromatic compounds have also received considerable attention. [9, 10] Oxidation reactions are of great importance in the chemical industry. Hydrogen peroxide and molecular oxygen are used as potent oxidant frequently. [11] But, their activities are kinetically low under many experimental conditions. In further studies such as design and development, transition metal complexes have attracted great attention due to catalyze the substrate oxidation effectively by hydrogen peroxide or molecular oxy- gen. [12] In addition to the use in organic synthesis, bleach catalyst based on hydrogen peroxide plays a major role for the pulp and paper production, waste water treatment and laundry for industrial and domestic applications, as well. [13] The main bleaching systems are based on destroying the stains on the fabric. This bleach process is carried out through oxidative [a] P. Sen, Prof. S. Z. Yildiz Department of Chemistry, Sakarya University, Faculty of Arts and Sciences, 54187, Sakarya, Turkey tel., + 90 264 2956136 E-mail: szy@sakarya.edu.tr [b] Assist. Prof. N. Dege Department of Physics Ondokuz Mayıs University, Faculty of Arts and Sciences, 55139 Atakum-Samsun, Turkey. [c] M. Atakay, Prof. B. Salih Department of Chemistry, Hacettepe University 06800 Ankara, Turkey. Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/slct.201601558 Full Papers DOI: 10.1002/slct.201601558 2643 ChemistrySelect 2017, 2, 2643 – 2650  2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim