History

Research groups of coordination chemistry- the historical outline*

For the beginning of coordination chemistry it can be recognised year 1890, when Alfred Werner (Nobel Prize in chemistry in year 1913) published his revolutionary theory propagating the idea of two types of valence existing in a large family of compounds (named later coordination compounds).

Only just 30 years later coordination chemistry became main object of investigations at the Technical University in Lwów (Poland), where a young analytical chemist Wiktor Jakób (1886-1971), became an associate professor of inorganic chemistry and was appointed the head of the Department of Inorganic Chemistry. The research area initiated by Wiktor Jakób attracted the attention of a group of young, talented students, some of which later became outstanding scientists, well-known in Poland such as Włodzimierz Trzebiatowski and Bogusława Jeżowska (later Jeżowska-Trzebiatowska) and in Ukraine (Cyryl Michalewicz).

Professor Wiktor Jakób in the 70’s of XXth century

The Second World War suddenly interrupted the research of W. Jakób and his students concerning among others the coordination compounds of newly discovered chemical element – rhenium (1925). After the Second World War some Polish scientists had moved from Lwów to Wrocław while W. Jakób had organized the Department of Inorganic Chemistry, first at the Technical University in Gliwice and next at the Jagiellonian University in Kraków. The first lecture in inorganic chemistry for students from the 1st year of chemistry, delivered by Prof. W. Jakób, who was still the head of Department of Inorganic Chemistry at Silesian Technical University in Gliwice took place in October 1949. Since autumn 1951 Prof. Jakób had been commuting from Gliwice to Kraków two or three times a week and since November 1951 he officially became the head of Department of Inorganic Chemistry at the Jagiellonian University.

Prof. Wiktor Jakób began at Jagiellonian University the scientific investigations in the field of coordination chemistry, at first in collaboration with his son Zbigniew Jakób (deceased prematurely in 1955), and then with other members of Department of Inorganic Chemistry such as: Krystyna Warchałowska (Dyrek), Mieczysław Dyrek, Maria Ogorzałek (1926-1960), Tadeusz Senkowski (1919-1989) and Adam Krawiec (1924-2004). Later (1954) Janina Chojnacka (1914-1977) had joined the group of Professor Jakób and afterwards Emilia Hejmo (1930-1998) and Maria Aleksandra Dąbrowska (Kanas) just after graduation as well as in 1955 Alina Kosińska (Samotus, 1932-2002) and Zofia Wilczewska (Stasicka), who during their graduation studies began research under professor Jakób’s supervision.

Shortly afterwards (1960-1964 ) first doctoral thesis from coordination chemistry were published on the Jagiellonian University. The first PhD degrees in coordination chemistry awarded: K. Warchałowska (Dyrek), T. Senkowski, J. Chojnacka, M. Dyrek, E. Hejmo, A. Dąbrowska (Kanas), A. Kosińska (Samotus) and Z. Wilczewska (Stasicka).

The research activity of Professor Jakób’s group was focused on: structure, electrochemistry, spectroscopy, thermal reactivity and photochemistry of coordination compounds of transition metals, mainly molybdenum, tungsten, chromium, manganese and cobalt. The undertaken research was pioneer and its value can only recently become appreciated. One subject area included in W. Jakób’s studies consisted of the spectroscopy and photochemistry of coordination compounds, which began as early as the 1920s and later was considerably developed in collaboration with Z. Jakób, A. Samotus, Z. Stasicka and T. Senkowski. The results showed new photochemical pathways proceeding in the octacyanometallates of molybdenum and tungsten and in nitrosylpentacyanomanganates. The research included chemical and physicochemical experiments, and some of the spectroscopic and mechanistic problems were solved in cooperation with theoretical chemist – Professor A. Gołębiewski.

The subject compounds included mostly the isoleptic or mixed ligand cyanide complexes, characterized by a large variety of coordination numbers, especially those unusually high. The investigations carried out by K. Dyrek concerned the nature of iodine bonding in chromium complexes had shed new light on properties of the Reinecke’s salt, which is currently used as an actinometer. Among the systems most intensively studied by W. Jakób and his students were cyanide complexes containing also the nitrosyl ligand, which are now in centre of interest as the NO carriers. In this subject, not only photochemistry but also electrochemistry and chemical behaviour were investigated, mostly in collaboration with T. Senkowski, E. Hejmo and A. Kanas. The results showed one of the first pathways of activation of small gaseous molecules, such as NO and O2. The studies of isopolymolybdates and isopolytungstates carried out by J. Chojnacka and M. Dyrek belonged to pioneer in the field of macromolecular compounds.

Despite the retirement (1960) Professor Jakób was still active in science and supervised his co-workers for last moments of his life (died in 1971).

In 1970 PhD Tadeusz Senkowski (qualified as assistant professor in 1968) became the head of the group of coordination chemistry and he continued research initiated by Professor Jakób. Then the group of coordination chemistry was separated into three main research groups:

  1. Group headed by Tadeusz Senkowski and Zofia Stasicka, where belonged: Emilia Hejmo, Mieczysław Dyrek, Tadeusz Jarzynowski (from 1969), Ewa Rzeszowska-Wasielewska (from 1972), Adam Marchaj (from 1973), Zygmunt Wołek (from 1975), Andrzej Karocki (from 1979), Grzegorz Stopa (from 1977), Grażyna Kurzawska-Stochel (from 1978), Anna Herdegen (from 1978) and Janusz Oszajca (from 1982).
  2. Group headed by Alina Samotus, where belonged: Aleksandra Kanas, Magdalena Dudek, Barbara Sieklucka, Ryszard Gryboś, Janusz Szklarzewicz and Jolanta Sosin.
  3. Group headed by Janina Chojnacka untill her death in 1977, with which Ewa Hodorowicz had cooperated. This group studied structure and properties of isopolytungstates with organic cations (E. Hodorowicz).

In 1984 the group of coordination chemistry has been divided on two parts: Coordination Chemistry I (headed by Zofia Stasicka, qualified as assistant professor in 1974 and title of professor in 1987, full professor from 1995) and Coordination Chemistry II (headed by A. Samotus, qualified as assistant professor in 1974 and title of professor in 1987, full professor from 1995).

Coordination Chemistry Group I

In years 1988-1994 research in the Coordination Chemistry Group I mainly focused on chemical and photochemical properties of cyanide and nitrosylcyanide complexes of transition metals from first transition series (E. Hejmo, T. Jarzynowski, A. Marchaj, G. Stochel, G. Stopa, J. Oszajca); correlation between electron structure and reactivity (E. Wasielewska, in collaboration with A. Gołębiewski from the Theoretical Chemistry Department at the Jagiellonian University); reactivity and photoactivation of molecular oxygen and nitric oxide in mixed-ligand cyanide complexes (A. Marchaj, G. Stochel, G. Stopa, J. Oszajca); kinetics and mechanisms of the reactions of pentacyanoferrate(II) and (III) using conventional and high pressure methods (G. Stochel in collaboration with R. van Eldik from the Erlangen-Nürnberg University); transition metals complexes with organic ligands of biological importance (T. Senkowski and M. Dyrek). In 80’s of XXth century the group had started research concerning utilization of mixed-ligand cyanide complexes of d-electron metals in photocatalysis and photoelectrocatalysis (Z. Stasicka, A. Marchaj, G. Stochel, G. Stopa, J. Oszajca, A. Karocki).

From 1994 the research in Coordination Chemistry Group I was carried out in two subgroups:

  1. Group headed by Zofia Stasicka, consisted of: Ewa Wasielewska, Grzegorz Stopa, Janusz Oszajca (from 1982), Konrad Szaciłowski (from 1995), Iwona Maciejowska, Joanna Kotaś, Wojciech Macyk (from 1997), Hung Bui Quang, Zygmunt Wołek and Andrzej Karocki. The research of this group was focused on thermal and photochemical reactivity of cyanide complexes of transition metals from the first transition series both homoleptic and mixed-ligand; photocatalysis and photoactivation of small molecules using coordination compounds; interaction of iron and chromium complexes with macromolecular compounds; role of light and coordination compounds in processes of environmental polution and its abatement. The group cooperated with Professor F. Wasgestian from the University in Cologne and with Professor M. Aresta from the University in Bari.
  2. Group headed by Grażyna Stochel (qualified as assistant professor in 1993, full professor from 2005), consisted of: Elwira Ilkowska (from 1991), Alicja Wanat (from 1996), Maria Wolak (from 1997) , Ewa Kuliś (from 1996) and Małgorzata Brindell (from 1999). The research of this group concerned bioinorganic and biomedical aspects of chemistry and photochemistry of metals from the first transition series (Fe, Co, Cu, Cr, Mn); biochemistry of small molecules (NO and CO); mechanisms and modelling of electron transfer process, substitution and addition in systems containing cellular reductants or S, N, O-nucleophilic reagents and metal complexes; role of light and coordination compounds in photomedicine (phototherapy and photodiagnostic); using high-pressure kinetics methods in the investigations of thermal and photochemical reactions of coordination compounds.

In 1998 Coordination Chemistry Group I had transformed into Coordination Compound and Bioinorganic Chemistry Physicochemistry Group (later the name was changed into Coordination and Bioinorganic Physicochemistry Group) and in 2003, after retirement of Professor Zofia Stasicka, Professor Grażyna Stochel (title of professor in 2001) became a head of the group. This group consisted of: Zofia Stasicka, Ewa Wasielewska, Grzegorz Stopa, Alicja Wanat, Konrad Szaciłowski, Wojciech Macyk, Maria Wolak, Małgorzata Brindell, Ewa Kuliś, Zygmunt Wołek, Janusz Oszajca, Andrzej Karocki continues research concerning mechanisms and practical aspects of thermal and photochemical reactivity of coordination compounds in homogeneous and heterogeneous systems. In the centre of their interest are coordination compounds and processes of catalytic, environmental, medical, material and nanotechnological importance. Research is focused on design and studies of potential photocatalysts, photosensitizers, molecular switches, logical gates, sensors, advanced materials for optoelectronics and nanoelectronics, self-cleaned surfaces, agents for environment protection, diagnostic agents and drugs. Part of research at the interdisciplinary nature is carried out in cooperation with Faculty of Biochemistry, Biophysics and Biotechnology as well as Collegium Medicum of the Jagiellonian University.

 

Coordination Chemistry Group II

Coordination Chemistry Group II headed by Alina Samotus in years 1984-2002 continued research concerning photochemistry of octacyanomolybdenum(IV/V) complexes (B. Sieklucka in collaboration with T. J. Kemp from Warwick University, United Kingdom) and structure and reactivity of mixed-ligand tetracyano complexes of molybdenium(IV) and tungsten(IV) (A. Kanas and M. Dudek). In the group also stereochemistry and phase transitions in octacyanomolybdenum(V) with organic cations were investigated (E. Hodorowicz, J. Szklarzewicz in collaboration with S. Hodorowicz from Department of Crystal Chemistry and Crystal Physics of the Jagiellonian University). Solubility of metallic silver in aerated ammonia solutions was studied (R. Gryboś) as well as structure of solid phases and equilibrium in solutions consisted of molybdates (VI) and citrate ions.

In 2002, after retirement of Professor A. Samotus Coordination Chemistry II had been divided on two groups: Coordination Chemistry Group headed by J. Szklarzewicz (qualified as assistant professor in 2002) and Inorganic Molecular Materials Group headed by B. Sieklucka (qualified as assistant professor in 1994, title of professor in 2004).

  1. Coordination Chemistry Group consisted of Ryszard Gryboś, Magdalena Dudek, Ewa Hodorowicz, Dariusz Matoga and Jolanta Tuz carried out investigations in the field of synthesis, kinetics, structure and reactivity of coordination compounds, mainly molybdenum, tungsten and vanadium. Their research is focused on: (i) mechanisms of reactions leading to incorporation of ligands, (ii) the unusual ligand reactivity arising from their coordination, (iii) synthesis of ligands directly on metal cent, and (iv) reactivity taking place on ligands. Practical aspect of this research includes using the coordination compounds as drugs (vanadium and molybdenum compounds acting as insulin mimetcs, R. Gryboś in collaboration with Collegium Medicum at the Jagiellonian University), catalysts and recently also in nonlinear optics, in creating nanocomposite and electronic systems.
  2. Inorganic Molecular Materials Group consisted of Robert Podgajny, Tomasz Korzeniak, Beata Nowicka and Paweł Przychodzeń carries out the research in the field of supramolecular coordination chemistry of polynuclear coordination compounds. The undergoing research concerns design, synthesis and characterisation of new magnetic and photomagnetic materials based on molecular building blocks with using of coordination compounds of d- and f-electron metals. The group research has nanotechnology practicable profile. Heterometallic compounds in the form of clusters or multidimensional coordinating networks can serve as carriers of magnetic memory or can be employed for construction of conductors and molecular switches, optical fibers or molecular magnets.

The family tree of coordination chemistry in Poland

1: Prof. Wiktor Jakób, 2: Prof. Cyryl Michalewicz, 3: Prof. Bogusława Jeżowska-Trzebiatowska, 4: Doc. Janina Chojnacka, 5: Doc. Tadeusz Senkowski, 6: Prof. Alina Samotus, 7: Prof. Zofia Stasicka, 8: Prof. Grażyna Stochel, 9: Prof. Barbara Sieklucka, 10: Dr. hab. Janusz Szklarzewicz (drawn by mgr inż. Zygmunt Wołek)

* The text is based in part on the article by Z. Stasicka, J. J. Ziółkowski “Origin and development of coordination chemistry in Poland – Introductory remarks” Coord. Chem. Rev. 2005, 249, 2133-2143.