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Perspective
The voyage of Goldberg: supramolecular chemistry and memories
Hatem M. Titi, and Sanjit Konar
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b00590 • Publication Date (Web): 11 Jun 2019
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The voyage of Goldberg: supramolecular chemistry
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and memories
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16 Hatem M. Titia,* and Sanjit Konarb,*
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19 aDepartment of Chemistry, McGill University, Montreal, QC, H3A 0B8, Canada; bDepartment of
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Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri,
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Bhopal 462 066, India
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30 We knew what we had, but we never thought we would lose Professor Israel Goldberg, legendary
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32 crystallographer, professor, mentor, and friend. This virtual special issue (VSI) in Crystal Growth
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34 & Design is dedicated to the memory of Professor Israel Goldberg who passed on February 18th,
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37 2018 and serves as a homage to his long-standing career in crystallography, crystal engineering
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39 and solid-state supramolecular chemistry and their applications.
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42 Prof. Israel Goldberg (Figure 1) was born on June 13, 1945 in Poland. After obtaining his B.Sc.,
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44 M.Sc. and Ph.D. (1974) degrees from Tel Aviv University, he took up a two-year post-doctoral
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47 position at UCLA. During that time, Prof. Goldberg conducted ground-breaking work in the field
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49 of solid-state supramolecular chemistry on the structures of various polycyclic ethers. In 1975,
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51 Prof. Goldberg joined the faculty of Tel Aviv University, and after being promoted to full professor
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in 1991, served as the head of the School of Chemistry from 1993 to 1997. He also held the
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56 Alexander and Clara Stransky Chair in Chemistry of Advanced Materials from 2009 to 2015.
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3 Throughout his illustrious career, Prof. Goldberg’s pioneering research in the fields of
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6 crystallography, crystal engineering, and supramolecular chemistry has been disseminated in the
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8 form of over 500 scientific papers published in the highest impact journals. His research, which
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10 was always at the forefront of new discoveries, revealed the ability to form new porphyrin
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assemblies as well as the discovery of new organic and organo-metallic materials in the solid state.
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15 Prof. Goldberg also took time out of his eminent research career to give back to the national and
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17 international scientific community as a member of the Israel Chemical Society, the American and
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European Crystallographic Associations and the Society of Porphyrins and Phthalocyanines.
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38 Figure 1. Prof. Israel Goldberg (1945-2018), the picture was taken by H.M. Titi during the 1st International
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40 Symposium on Halogen Bonding (ISXB-1), June 2014, Italy.
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It could be said that Prof. Goldberg’s career started when he solved his first crystal structure
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46 between 1969-1970 – that of the organic molecule (1)benzothieno(2,3-b)(1)benzothiophene,
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48 which was isolated through a simple reaction between sulfur and diphenylethylene.1 This would
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prove to be the first of many important steps in Prof. Goldberg’s career centered on the world of
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53 crystallography and supramolecular chemistry. Indeed, Prof. Goldberg subsequently completed
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55 his doctoral degree at Tel Aviv University studying “The influence of the molecular structure on
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3 crystal packing and thermal motion in charge-transfer compounds” under the supervision of a
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6 pioneering crystallographer and editor of Volume B for International Tables for Crystallography
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8 Prof. Uri Shmueli. As emphasized by the title of his thesis, Prof. Goldberg’s doctoral work
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10 elucidated the influence of the crystal packing and thermal parameters on the behavior of charge-
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transfer molecules and more specifically, co-crystals of tetracyanoquinodimethane and
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15 tetracyanoethylene.2,3 For many of us “modern and young” crystallographers, it is hard to digest
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17 the tremendous amount of work needed to solve the structure of even the simplest molecular
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complexes without today’s advanced computing methods. The structures in Prof. Goldberg’s thesis
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22 were characterized when techniques such as nuclear magnetic resonance (NMR) and X-ray
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24 diffraction were still in their infancy, free of high-tech software and computerized techniques
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26 available today. Moreover, the thesis did not only include new crystal structures but also molecules
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29 whose constrained refinements were extremely difficult to achieve using the technology of the
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31 day. These kind of refinements and precision disorder modeling as seen in the co-crystal
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33 tetracyanoethylene-naphthalene, reported in 1974, can be described as an elegant art. This co-
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crystal was first isolated by William and Wallwork in 1967 at room temprature,4 in which the
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38 naphthalene molecule exhibits high thermal motions (Figure 2a) and it was later refined using
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40 constraints by Goldberg and Shmueli (Figure 2b).5
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3 Figure 2. The naphthalene molecules described by (a) William and Wallwork, (b) modeled disorder of
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5 naphthalene by Goldberg and Shmueli and (c) the naphthalene molecule depicted without disorder for
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clarity.5 Adapted from ref. 5 with permission from The IUCr.
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11 Following the completion of his doctoral degree, Prof. Goldberg decided to pursue a post-
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13 doctoral position at UCLA. After his stay at UCLA, Prof. Goldberg rejoined Tel Aviv University
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15 as a faculty member, where he continued to study the crystallographic features of various
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18 polycyclic ethers and their host-guest interactions.6-9 Prof. Goldberg’s research as a university
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20 professor involved collaborations with notable scientists such as Donald J. Cram at UCLA, who
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22 shared the 1987 Nobel Prize in Chemistry together with Jean-Marie Lehn and Charles J. Pedersen.
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While giving his Nobel lecture and referencing his award-winning research, Cram stated: “By the
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27 end of 1986, Drs. K. N. Trueblood, C. B. Knobler, E. F. Maverick, and I. Goldberg, working at
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29 UCLA, had determined the crystal structures of over 50 complexes, and those of another 25 hosts.
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31 These crystal structures turned our faith into confidence.10 ” Figure 3 demonstrates an example of
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34 a cavitand forming host-guest interactions with CS2 entity determined by Goldberg during his
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36 work with Cram.11
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39 Although Prof. Goldberg’s achievements in crystallography and supramolecular chemistry are
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42 incredibly impressive, the humble scientist neither bragged about his accomplishments, nor his
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44 close relationships with distinguished scientists and Nobel laureates in various fields of research.
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46 He was a sharp, dedicated mentor with a great personality and a hearty sense of humor, yet never
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shied away from giving his students the constructive criticism they needed to grow as budding
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51 chemists. Working with Cram had a great influence and inspiration on Prof. Goldberg’s career,
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53 and eventually shaped the focus of his group’s research. As a result, Prof. Goldberg spent his career
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3 exploring the world of supramolecular synthons based on heterocyclic macrocycles in porphyrins
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6 and other small molecules, subjects which he was immensely passionate about.
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29 Figure 3: Illustration of the cavitand (Capped Sticks) hosting a CS2 (Ball and Stick) molecules. This crystal
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31 structure was solved by Goldberg during his collaboration with Cram (CSD ref. CUYXEZ10).11
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34 Prof. Goldberg brought this passion to his research on the solid-state chemistry of porphyrins
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37 through various non-covalent and coordination bonds. Among the 1200 crystal structures
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39 published by Prof. Goldberg in the Cambridge Structural Database (CSD)12, a third of these
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41 structures contain porphyrin building blocks. In 1991 he published the crystal structures of 34
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tetraarylporphyrin-based clathrates in collaboration with Charles E. Strouse.13 Prof. Goldberg thus
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46 became a pioneer in studying microporous structures based on porphyrin building units. Although
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48 porphyrins became the star molecules in his laboratory, Prof. Goldberg never hesitated to expand
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50 his research horizons into the design of other supramolecular materials such as coordination
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53 polymers, as well as hydrogen- and halogen-bonded (Figure 4) frameworks.14-20
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28 Figure 4. An example that indicates supramolecular chirality induced by inter-porphyrin Br⋯N halogen
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30 bonds reported by Goldberg, CSD ref. DEGREO.21
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In 2002, Prof. Goldberg organized the XII International Symposium on Supramolecular
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36 Chemistry (ISSC-XII) was held in Eilat, Israel, which can be considered as one of his major
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38 contributions to the supramolecular community. The ISSC was considered the largest and
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40 important meeting for supramolecular chemists worldwide, held biannually since the inaugural
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43 one in 1980 in Warsaw, Poland, and encompassing a wide variety of fundamental and applied
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45 topics in chemistry and materials science. In 2006, ISSC was combined with the International
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47 Symposium on Macrocyclic Chemistry (ISMC) in Victoria, Canada, and is now held yearly in
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different countries around the world as the International Symposium on Macrocyclic and
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52 Supramolecular Chemistry (ISMSC). ISSC-XII hosted participants from Asia (Japan, South
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54 Korea, India, China & Hong Kong), Europe (Moldova, Russia, Poland, Czech Republic, Germany,
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3 Netherlands, Switzerland, France, Italy, United Kingdom), Africa (Ghana) and North America
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6 (Canada, United States). Among the participants were the world-leading experts from different
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8 fields such as S. Stupp (USA), W. Hosseini (France), I. Williams (Hong Kong) and D. Soldatov
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10 (Canada), J. Lipkowski (Poland), K. Suwinska (Poland), J. Sessler (USA) and many others. 22
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As a student (H.M.T.) it was an honor to meet Prof. Goldberg for the first time in his office in
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16 the winter of 2009, as I was an impressionable student aspiring to pursue my master’s degree under
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18 his supervision at Tel Aviv University. I was very anxious that my application would be rejected,
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therefore losing my opportunity to start training as a crystallographer. As I think of that first
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23 conversation, I recall how he listened with open ears as I expressed my fears and dreams,
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25 reassuring me with his ability to mingle seriousness with humor. This was just the start of my
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27 exceptional voyage into the world of supramolecular chemistry with Prof. Goldberg. I will always
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30 appreciate the great guidance, outstanding support, continuous advice, and patience he had as a
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32 graduate supervisor and mentor. As his last Ph.D. student, I am grateful to Prof. Goldberg for all
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34 the knowledge he passed on to me, as well as the ideas and courage he instilled in me to step into
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the path of science. His ability to provide scientific leadership while allowing me to explore my
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39 ideas during my master and Ph.D. degrees provided me with the knowledge and independence that
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41 has shaped the scientist I am today. Regretfully, I can now never repay him for all those years of
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mentorship. For many years, Prof. Goldberg hid his illness from many friends and colleagues.
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46 However, his passion for science and education inspired him to continue working with students,
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48 colleagues, and collaborators without hesitation. Despite his health condition and until the last
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50 weeks of his life, he managed to support and leave his last touches as a supervisor on Mr. Yoel
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53 Friedman’s master’s thesis. This act of bravery shows Prof. Goldberg’s great dedication towards
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55 his students as well as his research and is something that we can all admire and aspire to emulate.
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3 AUTHOR INFORMATION
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7 Corresponding Authors:
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10 *Email: hatem.titi@mcgill.ca, skonar@iiserb.ac.in
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13 ACKNOWLEDGMENT
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We would like to thank all the contributors to this VSI for their help to honor the memory of a
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19 good colleague, a good scholar and a friend. We are also tremendously thankful to Robin and
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21 Mihaela Rogers for their patience and assistance in preparing this VSI. We also would like to thank
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Siting Ni for her great help during the preparation cover of art.
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27 REFERENCES
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30 1. Dayagi, S.; Goldberg, I.; Shmueli, U. Chemistry and structure of [1] benzothieno [2, 3-b][1]
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32 benzothiophene. Tetrahedron 1970, 26, 411-419.
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36 2. Goldberg, I.; Shmueli, U. Structure and Packing Arrangement of the π Complex of 7, 7, 8, 8-
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38 Tetracyanoquinodimethane and Phenazine. Nature Physical Science 1971, 234, 36.
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41 3. Goldberg, I.; U. Shmueli. Structure and packing arrangement of molecular compounds. II.(1: 1)
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44 7, 7, 8, 8‐Tetracyanoquinodimethane–dibenzo‐p‐dioxin. Acta Crystallogr., Sect. B: Struct. Sci.
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46 1973, 29, 432-440.
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49 4. Williams, R. M.; Wallwork, S. C. Molecular complexes exhibiting polarization bonding. IX.
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The crystal and molecular structure of the tetracyanoethylene–naphthalene complex. Acta
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54 Crystallographica 1967, 22, 899-906
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3 5. Shmueli, U.; Goldberg I. Structure and packing arrangement of molecular compounds. V.
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6 Constrained refinement of a disordered (1: 1) tetracyanoethylene–naphthalene structure. Acta
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8 Crystallogr., Sect. B: Struct. Sci. 1974, 30, 573-578.
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11 6. Goldberg, I. Structure and binding in molecular complexes of cyclic polyethers. I. 1, 4, 7, 10,
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14 13, 16‐Hexaoxacyclooctadecane (18‐crown‐6)–dimethyl acetylenedicarboxylate at –160° C. Acta
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16 Crystallogr., Sect. B: Struct. Sci. 1975, 31, 754-762.
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19 7. Goldberg, I. Structure and binding in molecular complexes of cyclic polyethers. II. Hydrogen
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bonding and ion pairing in a complex of a macrocyclic polydentate ligand with butylamine at 120
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24 K. Acta Crystallogr., Sect. B: Struct. Sci. 1975, 31, 2592-2600.
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27 8. Goldberg, I. Structure and binding in molecular complexes of cyclic polyethers. III. Host–guest
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29 interaction involving two assemblies of binding sites. Acta Crystallogr., Sect. B: Struct. Sci. 1977,
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32 33, 472-479.
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35 9. Goldberg, I. Structure and binding in molecular complexes of cyclic polyethers. 4.
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37 Crystallographic study of a chiral system: an inclusion complex of a macrocyclic ligand with
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40 phenylglycine methyl ester. J. Am. Chem. Soc. 1977, 99, 6049-6057.
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43 10. Cram, D. J. The design of molecular hosts, guests, and their complexes (Nobel lecture). Angew.
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45 Chem. Int. Ed. 1988, 27, 1009-1020; Science 1988, 240, 760-767.
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11. Cram, D. J.; Stewart, K. D.; Goldberg, I.; Trueblood, K. N. Complementary solutes enter
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51 nonpolar preorganized cavities in lipophilic noncomplementary media. J. Am. Chem. Soc. 1985,
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53 107, 2574-2575.
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3 12. Groom, C. R.; Bruno, I. J.; Lightfoot M. P.; Ward, S. C. The Cambridge structural database.
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6 Acta Crystallogr., Sect. B: Struct. Sci. 2016. B72, 171-179.
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9 13. Byrn, M. P.; Curtis, C. J.; Goldberg, I.; Hsiou, Y.; Khan, S. I.; Sawin, P. A.; Tendick, S. K.;
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11 Strouse, C. E. Porphyrin sponges: structural systematics of the host lattice. J. Am. Chem. Soc.
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1991, 113, 6549-6557.
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17 14. Titi, H. M.; Tripuramallu, B. K.; Goldberg, I. Porphyrin-based assemblies directed by non-
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19 covalent interactions: highlights of recent investigations. CrystEngComm 2016, 18, 3318-3339.
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15. Goldberg I. Crystal engineering of nanoporous architectures and chiral porphyrin assemblies.
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25 CrystEngComm 2008, 10, 637-645.
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28 16. Goldberg I. Metalloporphyrin Molecular Sieves. Chem. Eur. J. 2000, 6, 3863-3870.
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31 17. Goldberg I. Crystal engineering of porphyrin framework solids. Chem. Commun. 2005, 1243–
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34 1254.
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37 18. Tripuramallu, B. K. Titi, H. M.; Roy, S.; Verma, R.; Goldberg I. Ameliorated synthetic
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39 methodology for crystalline lanthanoid–metalloporphyrin open frameworks based on a multitopic
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octacarboxy-porphyrin scaffold: structural, gas sorption and photophysical properties.
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44 CrystEngComm 2016, 18, 515-520.
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47 19. Karmakar, A.; Goldberg I. Coordination polymers of flexible tetracarboxylic acids with metal
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ions. I. Synthesis of CH2- and (CH2)2-spaced bis(oxy)isophthalic acid ligands, and structural
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52 characterization of their polymeric adducts with lanthanoid ions. CrystEngComm, 2011, 13, 339-
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54 349.
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3 20. Diskin‐Posner, Y.; Dahal, S.; Goldberg I. Crystal Engineering of Metalloporphyrin Zeolite
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6 Analogues. Angew. Chem. 2000, 112, 1344-1348.
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9 21. Titi, H. M.; Karmakar, A.; Goldberg, I. J. Porphyrins Phthalocyanines 2011, 15, 1250-1257.
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12 22. Goldberg, I. IUCr Newsletter, 2003, 11, No.1; https://www.iucr.org/world/meeting-
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45 Professor Israel Goldberg (1945 -2018) an outstanding scientist and crystallographer with a
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warm personality
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